Polymerization process using pyridyldiamido compounds supported on organoaluminum treated layered silicate supports

ABSTRACT

This invention relates to a process to polymerize olefins comprising: i) contacting one or more olefins with a catalyst system comprising: 1) a support comprising an organoaluminum treated layered silicate and an inorganic oxide; and 2) a pyridyldiamido compound; and ii) obtaining olefin polymer having high molecular weight and layered silicate dispersed therein. Preferably the support is in the form of spheroidal particles.

CROSS REFERENCE TO RELATED APPLICATIONS

This invention claims priority to and the benefit of U.S. Ser. No.62/222,935, filed Sep. 24, 2015.

FIELD OF THE INVENTION

This invention relates to supported pyridyldiamido compounds useful forthe polymerization of olefins, in particular ethylene, where thecatalyst support comprises a layered silicate and an inorganic oxide.This invention also relates to polymerization processes using thesesupported pyridyldiamido compounds, in particular, gas phasepolymerization processes.

BACKGROUND OF THE INVENTION

Various types of polyethylenes are known in the art and, high density,low density, and linear low density polyethylenes are some of the mostuseful. Low density polyethylene is generally prepared at high pressureusing free radical initiators, or in gas phase processes usingZiegler-Natta or vanadium catalysts, and typically has a density in therange of 0.916 to 0.950 g/cm³. Typical low density polyethylene producedusing free radical initiators is known in the industry as “LDPE”. LDPEis also known as “branched” or “heterogeneously branched” polyethylenebecause of the relatively large number of long chain branches extendingfrom the main polymer backbone. Polyethylene in the same density range,i.e., 0.916 to 0.940 g/cm³, which is linear and does not contain longchain branching, is known as “linear low density polyethylene” (“LLDPE”)and is typically produced with conventional Ziegler-Natta catalysts orwith metallocene catalysts. Polyethylenes having still greater densityare the high density polyethylenes (“HDPEs”), i.e., polyethylenes havingdensities greater than 0.940 g/cm³, and are generally prepared withZiegler-Natta catalysts. Very low density polyethylenes (“VLDPEs”) arealso known. VLDPEs can be produced by a number of different processesyielding polyethylenes having a density less than 0.916 g/cm³, typically0.890 to 0.915 g/cm³ or 0.900 to 0.915 g/cm³.

A majority of global LDPE and LLDPE demand includes film, carrying bag,and sack applications. Some examples of these applications includeagricultural, multi-layer, and shrink films. LDPE, which is soft,ductile, and flexible, is additionally utilized for strong, elasticgoods, such as screw caps, lids, and coatings. There remains a demandfor LDPE and LLDPE in the global marketplace, and consequently there isa continued need for improvements that provide cost savings.

Some improvements include using a different catalyst system. Forexample, some work has been done to provide branched polymers having adensity of 0.940 g/cm³ or less using metallocene compounds.JP2011-089019A discloses a bridged metallocene in combination with acocatalyst (a modified clay mineral, an alkyl alumoxane or an ionizedionic compound) and an organoaluminum compound for olefin polymerizationwhich can produce a polyolefin which possesses long chain branching withhigh activity.

Pyridyl amines have been used to prepare Group 4 complexes which areuseful transition metal components for use in the polymerization ofalkenes, see for example US 2002/0142912; U.S. Pat. No. 6,900,321; andU.S. Pat. No. 6,103,657, where the ligands have been used in complexesin which the ligands are coordinated in a bidentate fashion to thetransition metal atom.

Other improvements have focused on the support technology. Alternativesupports for metallocene and single-site catalysts have been the subjectof numerous ongoing research projects. In particular, metallocenessupported on clay or ion-exchanged layered compounds have generated agreat deal of interest. Olefin polymerization catalysts using clay, claymineral, or acid/salt-treated (or a combination of both) ion-exchangelayered compounds, an organoaluminum compound and a metallocene ascomponents have been reported (see EP 0,511,665A2; EP 0,511,665B1; andU.S. Pat. No. 5,308,811). Likewise, U.S. Pat. No. 5,928,982 and U.S.Pat. No. 5,973,084 report olefin polymerization catalysts containing anacid or salt-treated (or a combination of both) ion exchange layeredsilicate, containing less than 1% by weight water, an organoaluminumcompound and a metallocene. Furthermore, WO 01/42320 A1 disclosescombinations of clay or clay derivatives as a catalyst support, anactivator comprising any Group 1-12 metal or Group 13 metalloid, otherthan organoaluminum compound, and a Group 3-13 metal complex. Also, U.S.Pat. No. 6,531,552B2 and EP 1,160,261 A1 report an olefin polymerizationcatalyst of an ion-exchange layered compound having particular acidstrength and acid site densities. US 2003/0027950 A1 reports an olefinpolymerization catalyst utilizing ion-exchange layered silicates with aspecific pore size distribution and having a carrier strength within aspecific range.

U.S. Pat. No. 7,220,695 discloses catalyst systems comprising, interalia, metallocene catalysts and supported activator systems comprisingan ion-exchange layered silicate, an organoaluminum compound, and aheterocyclic organic compound, see Example 7 et seq.

U.S. Pat. No. 6,559,090 discloses a coordinating catalyst systemcomprising at least one metallocene or constrained geometry pre-catalysttransition metal compound, (e.g., di-(n-butylcyclopentadienyl)zirconiumdichloride), at least one support-activator (e.g., spray driedsilica/clay agglomerate), and, optionally, at least one organometalliccompound (e.g., triisobutyl aluminum), in controlled amounts, andmethods for preparing the same.

Accordingly, there is a need for new processes to produce low cost LLDPEor HDPE over a wide molecular weight range. More specifically, there isa need for new supported catalyst systems, particularly supportedpyridyldiamido catalyst systems, to produce new polyethylenes, such ashigh molecular weight polyethylenes, which can be useful as a componentin bimodal high density PE resins for pipe applications, film, or blowmolding, particularly such with layered silicates dispersed therein. Itis further desirable that these new pyridyldiamido catalyst systems arerobust and have high productivity, particularly in gas phasepolymerization processes, and can even be used as a single componentsupported catalyst or in a mixed component catalyst system.

SUMMARY OF THE INVENTION

This invention relates to a process to polymerize olefins comprising: i)contacting olefins with a catalyst system comprising: 1) supportcomprising an organoaluminum treated layered silicate and an inorganicoxide and 2) pyridyldiamido compound represented by the Formula (A):

wherein:M* is a Group 4 metal;each E′ group is independently selected from carbon, silicon, orgermanium;each X′ is an anionic leaving group;L* is a neutral Lewis base;R′¹ and R′¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, and R′¹² areindependently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphino;n′ is 1 or 2;m′ is 0, 1, or 2; andtwo X′ groups may be joined together to form a dianionic group;two L* groups may be joined together to form a bidentate Lewis base;an X′ group may be joined to an L* group to form a monoanionic bidentategroup;R′⁷ and R′⁸ may be joined to form a ring; andR′¹⁰ and R′¹¹ may be joined to form a ring.

This invention also relates to a process to polymerize olefinscomprising: i) contacting olefins with a catalyst system comprising: 1)support comprising an organoaluminum treated layered silicate and aninorganic oxide and 2) pyridyldiamido compound represented by theFormula (A):

wherein:M* is a Group 4 metal;each E′ group is independently selected from carbon, silicon, orgermanium;each X′ is an anionic leaving group;L* is a neutral Lewis base;R′¹ and R′¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, and R′¹² areindependently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphino;n′ is 1 or 2;m′ is 0, 1, or 2; andtwo X′ groups may be joined together to form a dianionic group;two L* groups may be joined together to form a bidentate Lewis base;an X′ group may be joined to an L* group to form a monoanionic bidentategroup;R′⁷ and R′⁸ may be joined to form a ring; andR′¹⁰ and R′¹¹ may be joined to form a ring; andand ii) obtaining polyolefin composition, A, having an Mw of 1,000,000g/mol or more and comprising less than 5 wt %, based upon weight ofpolymer, of the layered silicate, where polyolefin composition A has: 1)no diffraction peak resulting from interlamellar spacing of theorganoaluminum treated layered silicate, and/or 2) a diffraction peakresulting from interlamellar spacing of the organoaluminum treatedlayered silicate of Z Angstroms or more, where Z=5X, where X is thediffraction peak resulting from interlamellar spacing of the supportbefore combination with the catalyst compound, as measured by wide anglex-ray scattering.

This invention also relates to a supported catalyst system comprising apyridyldiamido compound described above and a support comprising anorganoaluminum (preferably alkylaluminum) treated layered silicate andan inorganic oxide.

This invention also relates to supported catalyst systems comprisingpyridyldiamido compounds described above supported on particles of anagglomerate of an inorganic oxide and an organoaluminum (preferablyalkylaluminum) treated layered silicate, where the support has beenspray dried prior to contact with the organoaluminum.

This invention relates to catalyst systems comprising: 1) a supportcomprising an organoaluminum treated layered silicate and an inorganicoxide and 2) pyridyldiamido compound represented by the formuladescribed above.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a depiction of compounds A, B, C and D.

DETAILED DESCRIPTION OF THE INVENTION Definitions

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as set out inCHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985). Therefore, a “Group 4metal” is an element from Group 4 of the Periodic Table.

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gP/gcat/hr.“Catalyst activity” is a measure of how many grams of polymer areproduced using a polymerization catalyst comprising W g of catalyst(cat) and may be expressed by the following formula: P/W and expressedin units of gP/g (cat), and is typically used for batch processes.Catalyst activity may be converted to catalyst productivity by takinginto account the run time of the batch process: catalystproductivity=catalyst activity/T, where T is the run time in hours.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For the purposes of this invention and the claims thereto,when a polymer is referred to as “comprising an olefin,” the olefinpresent in the polymer is the polymerized form of the olefin. Forexample, when a copolymer is said to have an “ethylene” content of 35 wt% to 55 wt %, it is understood that the mer unit in the copolymer isderived from ethylene in the polymerization reaction and said derivedunits are present at 35 wt % to 55 wt %, based upon the weight of thecopolymer.

A “polymer” has two or more of the same or different mer units. A“homopolymer” is a polymer having mer units that are the same. A“copolymer” is a polymer having two or more mer units that are differentfrom each other. A “terpolymer” is a polymer having three mer units thatare different from each other. “Different,” as used to refer to merunits, indicates that the mer units differ from each other by at leastone atom or are different isomerically. Accordingly, the definition ofpolymer, as used herein, includes co- and ter-polymers and the like andthe definition of copolymer, as used herein, includes terpolymers andthe like. An ethylene polymer is a polymer comprising more than 50 mol %ethylene, a propylene polymer is a polymer comprising more than 50 mol %propylene, and so on.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, and Mz is z average molecular weight, wt % isweight percent, mol % is mole percent, vol % is volume percent and molis mole. Molecular weight distribution (MWD), also referred to aspolydispersity index (PDI), is defined to be Mw divided by Mn, Mw/Mn.Unless otherwise noted, all molecular weights (e.g., Mw, Mn, Mz) haveunits of g/mol. Unless otherwise noted, all melting points (T_(m)) areDSC second melt.

A “catalyst system” is a combination of at least one catalyst compound,at least one activator, at least one support material, and optionalco-activator. An “anionic ligand” is a negatively charged ligand whichdonates one or more pairs of electrons to a metal ion. A “neutral donorligand” is a neutrally charged ligand which donates one or more pairs ofelectrons to a metal ion.

The following abbreviations are used through this specification: dme is1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr ispropyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, iBu isisobutyl, tBu is tertiary butyl, p-tBu is para-tertiary butyl, nBu isnormal butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOALis tri(n-octyl)aluminum, MAO is methylalumoxane, p-Me is para-methyl, Bnis benzyl (i.e., CH₂Ph), THF (also referred to as thf) istetrahydrofuran, tol is toluene, EtOAc is ethyl acetate, and Cy iscyclohexyl.

Room temperature (RT) is 23° C. unless otherwise indicated.

Unless otherwise indicated, the term “substituted” means that a hydrogenhas been replaced with a heteroatom, a heteroatom-containing group, or ahydrocarbyl group. For example, bromo-cyclopentadiene is cyclopentadienesubstituted with a bromine group.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group”, “radical”, and “substituent” are also used interchangeably inthis document. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be a radical of carbon and hydrogen, preferably a C₁-C₁₀₀radical of carbon and hydrogen, that may be linear, branched, or cyclic,and when cyclic, aromatic or non-aromatic.

Substituted hydrocarbyl radicals are hydrocarbyl radicals in which atleast one hydrogen atom of the hydrocarbyl radical has been substitutedwith a heteroatom or heteroatom-containing group, such as a group havingat least one functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂,AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like, orwhere at least one heteroatom has been inserted within a hydrocarbylring.

The term “complex”, as used herein, is also often referred to ascatalyst precursor, pre-catalyst, catalyst, catalyst compound,transition metal compound, or transition metal complex. These words areused interchangeably. Activator and co-catalyst are also usedinterchangeably.

A scavenger is a compound that is typically added to facilitatepolymerization by scavenging impurities. Some scavengers may also act aschain transfer agents. Some scavengers may also act as activators andmay be referred to as co-activators. A co-activator, that is not ascavenger, may also be used in conjunction with an activator in order toform an active catalyst. In some embodiments, a co-activator can bepre-mixed with the transition metal compound to form an alkylatedtransition metal compound. Examples of scavengers include, but are notlimited to, trialkylaluminums, methylalumoxanes, modifiedmethylalumoxanes, MMAO-3A (Akzo Nobel), bis(diisobutylaluminum)oxide(Akzo Nobel), tri(n-octyl)aluminum, triisobutylaluminum, anddiisobutylaluminum hydride.

The term “aryl” or “aryl group” means a six-carbon aromatic ring and thesubstituted variants thereof, including but not limited to, phenyl,2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means anaryl group where a ring carbon atom (or two or three ring carbon atoms)has been replaced with a heteroatom, preferably N, O, or S.

The term “ring atom” means an atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring atoms andtetrahydrofuran has 5 ring atoms.

A “ring carbon atom” is a carbon atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring carbon atomsand para-methylstyrene also has six ring carbon atoms.

A heterocyclic ring is a ring having a heteroatom in the ring structureas opposed to a heteroatom substituted ring where a hydrogen on a ringatom is replaced with a heteroatom. For example, tetrahydrofuran is aheterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatomsubstituted ring.

Aromatic means a cyclic hydrocarbyl with conjugated double bonds, suchas benzene or cyclopentadiene.

As used herein, the term “aromatic” also refers to pseudoaromatic cyclicgroups which are cyclic substituents that have similar properties andstructures (nearly planar) to aromatic ligands, but are not bydefinition aromatic.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

The term “agglomerate” as used herein refers to a material comprising anassembly, of primary particles held together by adhesion, i.e.,characterized by weak physical interactions such that the particles caneasily be separated by mechanical or chemical forces.

Embodiments

This invention relates to catalyst systems comprising: 1) a supportcomprising an organoaluminum treated layered silicate and an inorganicoxide and 2) pyridyldiamido compound represented by the Formula (A)below.

This invention also relates to a process to polymerize olefinscomprising: i) contacting olefins with catalyst systems comprising: 1) asupport comprising an organoaluminum treated layered silicate and aninorganic oxide and 2) pyridyldiamido compound represented by theFormula (A):

wherein:M* is a Group 4 metal (preferably hafnium);each E′ group is independently selected from carbon, silicon, orgermanium (preferably carbon);each X′ is an anionic leaving group (preferably alkyl, aryl, hydride,alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate,alkylsulfonate);L* is a neutral Lewis base (preferably ether, amine, thioether);R′¹ and R′¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups (preferablyaryl groups);R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, and R′¹² areindependently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphino;n′ is 1 or 2;m′ is 0, 1, or 2; andtwo X′ groups may be joined together to form a dianionic group;two L* groups may be joined together to form a bidentate Lewis base;an X′ group may be joined to an L* group to form a monoanionic bidentategroup;R′⁷ and R′⁸ may be joined to form a ring (preferably an aromatic ring,preferably a six-membered aromatic ring with the joined R′⁷R′⁸ groupbeing —CH═CHCH═CH—); andR′¹⁰ and R′¹¹ may be joined to form a ring (preferably a five-memberedring with the joined R′¹⁰R′¹¹ group being —CH₂CH₂—, or a six memberedring with the joined R′¹⁰R′¹¹ group being —CH₂CH₂CH₂—).

This invention also relates to a process to polymerize olefinscomprising contacting olefins with a catalyst system comprisingpyridyldiamido compound represented by the Formula (I), (II) or (III),as described herein, deposited on a support comprising organoaluminumtreated layered silicate and an inorganic oxide.

This invention further relates to a process to polymerize olefinscomprising: i) contacting olefins with catalyst systems comprising: 1)support comprising an organoaluminum treated layered silicate supportand an inorganic oxide and 2) pyridyldiamido compound represented by thefollowing Formula (I), (II) or (III):

wherein:M is a Group 4 metal;Z is —(R¹⁴)_(p)C—C(R¹⁵)_(q)—,where R¹⁴ and R¹⁵ are independently selected from the group consistingof hydrogen, hydrocarbyls, and substituted hydrocarbyls, and whereinadjacent R¹⁴ and R¹⁵ groups may be joined to form an aromatic orsaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ringcan join to form additional rings,p is 0, 1 or 2, andq is 0, 1 or 2;R¹ and R¹¹ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R² and R¹⁰ are each, independently, -E(R¹²)(R¹³)— with E being carbon,silicon, or germanium, and each R¹² and R¹³ being independently selectedfrom the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl,amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino, R¹²and R¹³ may be joined to each other or to R¹⁴ or R¹⁵ to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R¹² and R¹³ may be joined to forma saturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings;R³, R⁴, and R⁵ are independently selected from the group consisting ofhydrogen, hydrocarbyls (such as alkyls and aryls), substitutedhydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and whereinadjacent R groups (R³ & R⁴ and/or R⁴ & R⁵) may be joined to form asubstituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring atoms and where substitutions on the ringcan join to form additional rings;L is an anionic leaving group, where the L groups may be the same ordifferent and any two L groups may be linked to form a dianionic leavinggroup;n is 1 or 2;L′ is a neutral Lewis base; andw is 0, 1, or 2.

wherein:R⁶, R⁷, R⁸, and R⁹ are independently selected from the group consistingof hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen,amino, and silyl, and wherein adjacent R groups (R⁶& R⁷ and/or R⁷& R⁸and/or R⁸& R⁹, and/or R⁹& R¹⁰) may be joined to form a saturated,substituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring carbon atoms and where substitutions on thering can join to form additional rings; and M, L, L′, w, n, R¹, R², R³,R⁴, R⁵, R¹⁰, and R¹¹ are as defined above in Formula (I); and

wherein:R¹⁶ and R¹⁷ are independently selected from the group consisting ofhydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen,amino, and silyl, and wherein adjacent R groups (R⁶ & R⁷ and/or R⁷ & R¹⁶and/or R¹⁶ & R¹⁷, and/or R⁸ & R⁹) may be joined to form a saturated,substituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring carbon atoms and where substitutions on thering can join to form additional rings; and M, L, L′, w, n, R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are as defined above in Formula (I)and (II); andii) obtaining polyolefin composition, A, having an Mw of 1,000,000 g/molor more and comprising less than 5 wt %, based upon weight of polymer,of the layered silicate, where polyolefin composition A has: 1) nodiffraction peak resulting from interlamellar spacing of theorganoaluminum treated layered silicate, and/or 2) a diffraction peakresulting from interlamellar spacing of the organoaluminum treatedlayered silicate of Z Angstroms or more, where Z=5X, where X is thediffraction peak resulting from interlamellar spacing of the supportbefore combination with the catalyst compound, as measured by wide anglex-ray scattering.

This invention also relates to a process to prepare high molecularweight (Mw of 1,000,000 g/mol or more) ethylene polymers, preferablyhaving excellent bulk density (0.25 g/cc or more), preferably withoutusing additional activator such as an alumoxane and or anon-coordinating anion, comprising contacting ethylene and optionalcomonomer with a catalyst system comprising pyridyldiamido compoundrepresented by the Formula A, (I), (II) or (III), as described herein,deposited on a support comprising organoaluminum treated layeredsilicate and an inorganic oxide.

This invention also relates to any of the above processes where thesupport and or the supported catalyst system is present in the form ofspherioid particles, preferably having an average particle size (D50) of20 to 180 microns, alternately 55 to 180 microns, and a surface area ofabout 100 to about 200 m²/g and a pore volume of about 0.1 to about 0.4cc/g.

This invention also relates to any of the above processes where thesupport and/or the supported catalyst system have an average aspectratio (L/W) of 1 to 1.7 (alternately 1 to 1.6, alternately 1 to 1.5,alternately 1 to 1.4, alternately 1 to 1.3, and alternately 1 to 1.2).

Average aspect ratio of the support and or supported catalyst systems isdetermined by averaging the aspect ratio (length versus width) ofmultiple particles as shown in Scanning Electron Micrographs. SeveralSEM photographs of the sample are taken and 35 particles of layeredsilicate are identified and measured. For each of the 35 particles, thelongest dimension is identified by drawing a line between the two pointsat the edge of the particle which are the furthest apart (“length”).Then the shortest dimension is identified by drawing a line between thetwo points at the edge of the particle which are the least distanceapart (“width”). Length is then divided by width to obtain aspect ratio.The average aspect ratio is calculated as the arithmetical mean based onthe aspect ratio of the 35 particles. Image-Pro Plus™ v 7.0.0 is usedfor image analysis.

When selecting the 35 particles for analysis: 1) only particles whichare entirely in the field of view are chosen for analysis; and 2)particles which exhibit signs of damage such as rough fracture surfacesdue to handling are not included in the analysis.

This invention also relates to any of the above processes where thesupport and/or the supported catalyst system is present in the form ofspherioid particles, has an average aspect ratio (L/W) of 1 to 1.7(alternately 1 to 1.6, alternately 1 to 1.5, alternately 1 to 1.4,alternately 1 to 1.3, alternately 1 to 1.2); has an average particlesize (D50) of 20 to 180 microns, alternately 55 to 180 microns, has asurface area of about 100 to about 200 m²/g and has a pore volume ofabout 0.1 to about 0.4 cc/g.

Alternately, the catalyst system has an average aspect ratio (L/W) of 1to 1.7, has an average particle size (D50) of 20 to 180 microns, and hasa pore volume of about 0.1 to about 0.4 cc/g.

Pyridyldiamido Transition Metal Complex

The term “pyridyldiamido complex” or “pyridyldiamide complex” or“pyridyldiamido catalyst” or pyridyldiamide catalyst” refers to a classof coordination complexes described in U.S. Pat. No. 7,973,116B2, US2012/0071616A1, US 2011/0224391A1, and US 2011/0301310A1, US2014/0221587A1, US 2014/0256893A1, US 2014/0316089A1, US 2015/0141590A1,and US 2015/0141601A1 that feature a dianionic tridentate ligand that iscoordinated to a metal center through one neutral Lewis basic donor atom(e.g., a pyridine group) and a pair of anionic amido or phosphido (i.e.,deprotonated amine or phosphine) donors. In these complexes, thepyridyldiamido ligand is coordinated to the metal with the formation ofone five-membered chelate ring and one seven-membered chelate ring. Itis possible for additional atoms of the pyridyldiamido ligand to becoordinated to the metal without affecting the catalyst function uponactivation; an example of this could be a cyclometalated substitutedaryl group that forms an additional bond to the metal center.

In one aspect of the invention, the supported catalyst system comprisesa pyridyldiamido transition metal complex represented by the Formula(A):

wherein:M* is a Group 4 metal (preferably hafnium);each E′ group is independently selected from carbon, silicon, orgermanium (preferably carbon);each X′ is an anionic leaving group (preferably alkyl, aryl, hydride,alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate,alkylsulfonate);L* is a neutral Lewis base (preferably ether, amine, thioether);R′¹ and R′¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups (preferablyaryl);R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, and R′¹² areindependently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphino;n′ is 1 or 2;m′ is 0, 1, or 2; andtwo X′ groups may be joined together to form a dianionic group;two L* groups may be joined together to form a bidentate Lewis base;an X′ group may be joined to an L* group to form a monoanionic bidentategroup;R′⁷ and R′⁸ may be joined to form a ring (preferably an aromatic ring, asix-membered aromatic ring with the joined R′⁷R′⁸ group being—CH═CHCH═CH—); andR′¹⁰ and R′¹¹ may be joined to form a ring (preferably a five-memberedring with the joined R′¹⁰R′¹¹ group being —CH₂CH₂—, a six-membered ringwith the joined R′¹⁰R′¹¹ group being —CH₂CH₂CH₂—).

In any embodiment described herein, M* is preferably Zr, or Hf,preferably Hf.

In any embodiment described herein, the R′ groups above (R′¹, R′², R′³,R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹ R′¹², and R′¹³) preferablycontain up to 30, preferably no more than 30 carbon atoms, especiallyfrom 2 to 20 carbon atoms.

In a preferred embodiment of the invention, R′¹ is selected from phenylgroups that are variously substituted with between zero to fivesubstituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino,aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomersthereof.

In any embodiment described herein, preferably R′¹ and R′¹³ areindependently selected from phenyl groups that are variously substitutedwith between zero to five substituents that include F, Cl, Br, I, CF₃,NO₂, alkoxy, dialkylamino, aryl, and alkyl groups with between one toten carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, and isomers thereof.

In any embodiment described herein, preferably E is carbon, and R′¹ andR′¹³ are independently selected from phenyl groups that are variouslysubstituted with between zero to five substituents that include F, Cl,Br, I, CF₃, NO₂, alkoxy, dialkylamino, hydrocarbyl, and substitutedhydrocarbyls, groups with from one to ten carbons.

In any embodiment described herein, preferably R′¹ and R′¹³ are selectedfrom aryl or alkyl groups containing from 6 to 30 carbon atoms,especially phenyl groups. It is preferred that R′¹ and R′¹³ be chosenfrom aryl or alkyl groups and that R′², R′³, R′¹¹, and R′¹², beindependently chosen from hydrogen, alkyl, and aryl groups, such asphenyl. The phenyl groups may be alkyl substituted. The alkylsubstituents may be straight chain alkyls, but include branched alkyls.

Preferably, each R′¹ and R′¹³ is a substituted phenyl group with eitherone or both of R² and R¹¹ being substituted with a group containingbetween one to ten carbons. Some specific examples would include, R¹ andR¹³ being chosen from a group including 2-methylphenyl,2-isopropylphenyl, 2-ethylphenyl, 2,6-dimethylphenyl, mesityl,2,6-diethylphenyl, and 2,6-diisopropylphenyl.

In a preferred embodiment, R′⁷ and R′⁸ may be joined to form a four- toten-membered ring. One example has the R′⁷R′⁸ group being —CH═CHCH═CH—,with the formation of an aromatic six-membered ring.

In a preferred embodiment, R′¹⁰ and R′¹¹ may be joined to form a four-to ten-membered ring. One specific example has the R′¹⁰R′¹¹ group being—CH₂CH₂—, with the formation of a five-membered ring. Another examplehas the R′¹⁰R′¹¹ being —CH₂CH₂CH₂—, with the formation of a six-memberedring.

In a preferred embodiment, E′ is carbon.

In a preferred embodiment, R′² is an aromatic hydrocarbyl groupcontaining between 6 to 12 carbon atoms and R′¹³ is a saturatedhydrocarbon containing between 3 to 12 carbon atoms. A specific examplehas R′²=2-isopropylphenyl and R′¹³=cyclohexyl.

In any embodiment described herein, R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸,R′⁹, R′¹⁰, R′¹¹, and R′¹² may be hydrogen or alkyl from 1 to 4 carbonatoms. Preferably 0, 1, or 2 of R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹,R′¹⁰, R′¹¹, and R′¹² are alkyl substituents.

In any embodiment described herein, preferably X′ is selected fromalkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide,triflate, carboxylate, alkylsulfonate, alkoxy, amido, hydrido, phenoxy,hydroxy, silyl, allyl, alkenyl, and alkynyl.

In any embodiment described herein, preferably L* is selected fromethers, thio-ethers, amines, nitriles, imines, pyridines, andphosphines, preferably ethers.

In one aspect of the invention, the supported catalyst system comprisesa pyridyldiamido transition metal complex represented by the Formula(I):

M is a Group 4 metal, preferably a group 4 metal, more preferably Ti, Zror Hf;Z is —(R¹⁴)_(p)C—C(R¹⁵)_(q)—, where R¹⁴ and R¹⁵ are independentlyselected from the group consisting of hydrogen, hydrocarbyls, andsubstituted hydrocarbyls, (preferably hydrogen and alkyls), and whereinadjacent R¹⁴ and R¹⁵ groups may be joined to form an aromatic orsaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ringcan join to form additional rings,p is 1 or 2, andq is 1 or 2;R¹ and R¹¹ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups (preferablyalkyl, aryl, heteroaryl, and silyl groups);R² and R¹⁰ are each, independently, -E(R¹²)(R¹³)— with E being carbon,silicon, or germanium, and each R¹² and R¹³ being independently selectedfrom the group consisting of hydrogen, hydrocarbyl, and substitutedhydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino(preferably hydrogen, alkyl, aryl, alkoxy, silyl, amino, aryloxy,heteroaryl, halogen, and phosphino), R¹² and R¹³ may be joined to eachother or to R¹⁴ or R¹⁵ to form a saturated, substituted or unsubstitutedhydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms andwhere substitutions on the ring can join to form additional rings, orR¹² and R¹³ may be joined to form a saturated heterocyclic ring, or asaturated substituted heterocyclic ring where substitutions on the ringcan join to form additional rings;R³, R⁴, and R⁵ are independently selected from the group consisting ofhydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy,halogen, amino, and silyl, (preferably hydrogen, alkyl, alkoxy, aryloxy,halogen, amino, silyl, and aryl), and wherein adjacent R groups (R³ & R⁴and/or R⁴ & R⁵) may be joined to form a substituted or unsubstitutedhydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ringatoms and where substitutions on the ring can join to form additionalrings;L is an anionic leaving group, where the L groups may be the same ordifferent and any two L groups may be linked to form a dianionic leavinggroup;n is 1 or 2;L′ is a neutral Lewis base; andw is 0, 1, or 2.

In another preferred embodiment, Z is defined as an aryl so that thecomplex is represented by the Formula (II):

wherein:R⁶, R⁷, R⁸, and R⁹ are independently selected from the group consistingof hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen,amino, and silyl, and the pairs of positions, and wherein adjacent Rgroups (R⁶& R⁷, and/or R⁷& R⁸, and/or R⁸& R⁹, and/or R⁹& R¹⁰) may bejoined to form a saturated, substituted or unsubstituted hydrocarbyl orheterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atomsand where substitutions on the ring can join to form additional rings;andM, L, L, w, n, R¹, R², R³, R⁴, R⁵, R⁶, R¹⁰, and R¹¹ are as definedabove.

In a more preferred embodiment, the complexes of this invention arerepresented by the Formula (III):

wherein:R¹⁶ and R¹⁷ are independently selected from the group consisting ofhydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen,amino, and silyl, and wherein adjacent R groups (R⁶ & R⁷ and/or R⁷ & R¹⁶and/or R¹⁶ & R¹⁷, and/or R⁸ & R⁹) may be joined to form a saturated,substituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring carbon atoms and where substitutions on thering can join to form additional rings; and M, L, L′, w, n, R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are defined as above.

In any embodiment of Formula I, II or III described herein, M ispreferably Ti, Zr, or Hf, preferably HF or Zr.

In any embodiment of Formula I, II, or III described herein, the Rgroups above (R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶ and R¹⁷) preferably contain up to 30 carbon atoms,preferably no more than 30 carbon atoms, especially from 2 to 20 carbonatoms.

In any embodiment of Formula I, II, or III described herein, preferablyR¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², to R¹³ contain up to30 carbon atoms, especially from 2 to 20 carbon atoms.

In a preferred embodiment of the invention, R¹ is selected from phenylgroups that are variously substituted with between zero to fivesubstituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino,aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomersthereof.

In any embodiment of Formula I, II, or III described herein, preferablyR¹ and R¹¹ are independently selected from phenyl groups that arevariously substituted with between zero to five substituents thatinclude F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkylgroups with between one to ten carbons, such as methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.

In any embodiment of Formula I, II, or III described herein, preferablyE is carbon, and R¹ and R¹¹ are independently selected from phenylgroups that are variously substituted with between zero to fivesubstituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino,hydrocarbyl, and substituted hydrocarbyls, groups with from one to tencarbons.

In any embodiment of Formula I, II, or III described herein, preferablyR¹ and R¹¹ are selected from aryl or alkyl groups containing from 6 to30 carbon atoms, especially phenyl groups. It is preferred that R¹ andR¹¹ be chosen from aryl or alkyl groups and that R¹², R¹³, R¹⁴, and R¹⁵,be independently chosen from hydrogen, alkyl, and aryl groups, such asphenyl. The phenyl groups may be alkyl substituted. The alkylsubstituents may be straight chain alkyls, but include branched alkyls.

Preferably, each R¹ and R¹¹ is a substituted phenyl group with eitherone or both of the carbons adjacent to the carbon joined to the amidonitrogen being substituted with a group containing between one to tencarbons. Some specific examples would include R¹ and R¹¹ being chosenfrom a group including 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl,2,6-dimethylphenyl, mesityl, 2,6-diethylphenyl, and2,6-diisopropylphenyl.

In any embodiment of Formula I, II, or III described herein, R² ispreferably selected from moieties where E is carbon, especially a moiety—C(R¹²)(R¹³)— where R¹² is hydrogen and R¹³ is an aryl group or a benzylgroup (preferably a phenyl ring linked through an alkylene moiety suchas methylene to the C atom). The phenyl group may then be substituted asdiscussed above. Useful R² groups include CH₂, CMe₂, SiMe₂, SiEt₂,SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂, Si(alkyl)₂, CH(aryl), CH(Ph), CH(alkyl),and CH(2-isopropylphenyl).

In any embodiment of Formula I, II, or III described herein, R¹⁰ ispreferably selected from moieties where E is carbon, especially a moiety—C(R¹²)(R¹³)— where R¹² is hydrogen and R¹³ is an aryl group or a benzylgroup (preferably a phenyl ring linked through an alkylene moiety suchas methylene to the C atom). The phenyl group may then be substituted asdiscussed above. Useful R¹⁰ groups include CH₂, CMe₂, SiMe₂, SiEt₂,SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂, Si(alkyl)₂, CH(aryl), CH(Ph), CH(alkyl),and CH(2-isopropylphenyl).

In any embodiment of Formula I, II or III described herein R¹⁰ and R²are selected from CH₂, CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂,Si(aryl)₂, Si(alkyl)₂, CH(aryl), CH(Ph), CH(alkyl), andCH(2-isopropylphenyl).

In any embodiment of Formula I, II, or III described herein, R³, R⁴, R⁵,R⁶, R⁷, R⁸, and R⁹ may be hydrogen or alkyl from 1 to 4 carbon atoms.Preferably 0, 1, or 2 of R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are alkylsubstituents.

In any embodiment of Formula I, II, or III described herein, R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹², R¹³, R¹⁴, and R¹⁵ are, independently, hydrogen, aC₁ to C₂₀ alkyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof), ora C₅ to C₄₀ aryl group (preferably a C₆ to C₂₀ aryl group, preferablyphenyl or substituted phenyl or an isomer thereof, preferably phenyl,2-isopropylphenyl, or 2-tertbutylphenyl).

In any embodiment of Formula I, II, or III described herein, preferablyL is selected from halide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy,hydroxy, silyl, allyl, alkenyl, and alkynyl.

In any embodiment of Formula I, II, or III described herein, preferablyL′ is selected from ethers, thio-ethers, amines, nitriles, imines,pyridines, and phosphines, preferably ethers.

The pyridyldiamido-metal complex is coordinated at the metal center as atridentate ligand through two amido donors and one pyridyl donor. Themetal center, M or M*, is a transition metal from Group 4. While in itsuse as a catalyst, according to current theory, the metal center ispreferably in its four valent state, it is possible to create compoundsin which M has a reduced valency state and regains its formal valencystate upon preparation of the catalyst system by contacting with anactivator (e.g., the organoaluminum treated layered silicate).Preferably, in addition to the pyridyldiamido ligand, the metal M or M*is also coordinated to n number of anionic ligands, with n being from 1or 2. The anionic donors are typically halide or alkyl, but a wide rangeof other anionic groups are possible, including some that are covalentlylinked together to form molecules that could be considered dianionic,such as oxalate. For certain complexes, it is likely that up to threeneutral Lewis bases (L or L*), typically ethers, could also becoordinated to the metal center. In a preferred embodiment, w is 0, 1,or 2.

In a preferred embodiment, L or L* may be selected from halide, alkyl,aryl, alkoxy, amido, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl,and alkynyl. The selection of the leaving groups depends on thesynthesis route adopted for arriving at the complex and may be changedby additional reactions to suit the later activation method inpolymerization. For example, a preferred L or L* group is alkyl whenusing non-coordinating anions such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)-borate or tris(pentafluorophenyl)borane. Inanother embodiment, two L or two L* groups may be linked to form adianionic leaving group, for example oxalate.

In a preferred embodiment, X may be selected from halide, alkyl, aryl,alkoxy, amido, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl, andalkynyl. The selection of the leaving groups depends on the synthesisroute adopted for arriving at the complex and may be changed byadditional reactions to suit the later activation method inpolymerization. For example, a preferred X is alkyl when usingnon-coordinating anions such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)-borate or tris(pentafluorophenyl)borane. Inanother embodiment, two X groups may be linked to form a dianionicleaving group, for example, oxalate.

In another embodiment, each L* is independently selected from the groupconsisting of ethers, thio-ethers, amines, nitriles, imines, pyridines,and phosphines, preferably ethers.

Preferred compounds useful in catalyst mixtures herein include thepyridyldiamide complexes A through D in FIG. 1.

Complex Synthesis

A typical synthesis of the pyridyldiamido complexes is reaction of theneutral pyridyldiamine ligand with a metalloamide, such asHf(NMe₂)₂Cl₂(1,2-dimethoxyethane), Zr(NMe₂)₄, Zr(NEt₂)₄, Hf(NMe₂)₄, andHf(NEt₂)₄. Another synthesis route for the pyridyldiamido complexes isthe reaction of the neutral pyridyldiamine ligand precursors with anorganolithium reagent to form the dilithio pyridyldiamido derivativefollowed by reaction of this species with either a transition metalsalt, including ZrC₁₄, HfC₁₄, ZrCl₄(1,2-dimethoxyethane),HfCl₄(1,2-dimethoxyethane), ZrCl₄(tetrahydrofuran)₂,HfCl₄(tetrahydrofuran)₂, ZrBn₂Cl₂(OEt₂), HfBn₂Cl₂(OEt₂). Anotherpreferred synthesis route for the pyridyldiamido complexes is reactionof the neutral pyridyldiamine ligands with an organometallic reactant,such as ZrBn₄, ZrBn₂Cl₂(OEt₂), Zr(CH₂SiMe₃)₄, Zr(CH₂CMe₃)₄, HfBn₄,HfBn₂Cl₂(OEt₂), Hf(CH₂SiMe₃)₄, Hf(CH₂CMe₃)₄.

The general synthetic routes used for the complexes presented herein aredescribed in US 2014/0221587A1 and US 2015/0141601A1.

Catalyst Systems

The term “catalyst system” includes transition metal complex/activatorpair(s). When “catalyst system” is used to describe such pair(s) beforeactivation, it means the unactivated catalyst complex (pre-catalyst)together with an activator (e.g., the organoalumimun treated layeredsilicate) and, optionally, a co-activator. When it is used to describesuch a pair after activation, it means the activated complex and theactivator or other charge-balancing moiety. The transition metalcompound may be neutral, as in a pre-catalyst, or a charged species witha counter ion as in an activated catalyst system.

The complexes described herein may be used in combination with one ormore support-activators (e.g., the organoalumimun treated layeredsilicates described herein, which act as both supports and activators)for olefin polymerization, such as for ethylene-based polymers orpropylene-based polymers, including ethylene-octene polymerization.

In a preferred embodiment, this invention also relates to supportedcatalyst systems comprising: (i) at least one pyridyldiamido compoundrepresented by Formula (I), (II), (III) as described above; (ii) asupport comprising an agglomerate of organoaluminum (preferablyalkylaluminum) treated layered silicate material and inorganic oxide;and (iii) optionally, a co-catalyst. The pyridyldiamido catalystcompound may be any of the compounds described above. The organoaluminum(preferably alkylaluminum) treated layered silicate and optionalco-catalyst/scavenger are discussed below.

Typically, catalyst is present on the support at from 0.01 wt % to 1 wt%, preferably 0.1 to 0.5 wt % of Ti, Zr, or Hf, based upon the weight ofthe catalyst, any activator, and support.

Layered Silicates

This invention relates to catalyst systems comprising organoaluminum(such as alkyl aluminum) treated layered silicates. The layered silicatemay be an ion exchange layered silicate.

Preferred ion-exchange layered silicates useful in the present inventionare silicate compounds having a crystal structure wherein layers formedby strong ionic and covalent bonds are laminated in parallel with weakionic bonding, and the ions contained between the layers areexchangeable. Most ion-exchange layered silicates naturally occur as themain component of clay minerals, but these ion-exchange layeredsilicates may be artificially synthesized materials. Preferredion-exchange layered silicates useful in this invention include naturalor synthetic montmorillonite, nontronite, beidellite, volkonskoite,laponite, hectorite, saponite, sauconite, stevensite, vermiculite,halloysite, aluminate oxides, bentonite, kaolinite, dickite, smecticclays, mica, magadiite, kenyaite, octosilicate, kanemite, makatite,attapulgite, sepiolite, zeolitic layered materials (such as ITQ-2,MCM-22, and ferrierite precursors) and mixtures thereof. In a preferredembodiment, the ion-exchange layered silicate is acidified (bycontacting with an acid, such as sulfuric acid, hydrochloric acid, acarboxylic acid, an amino acid, or the like) or otherwise chemicallytreated (see U.S. Pat. No. 6,559,090, especially columns 25 to 27).

Preferred ion-exchange layered silicates useful in this inventioninclude those having a 1:1 type structure or a 2:1 type structure.Examples of the ion-exchange layered silicate include layered silicateshaving a 1:1 type structure or a 2:1 type structure as described in“Clay Mineralogy” written by R. E. Grim (published by McGraw Hill in1968) and “Chemistry of Clays and Clay Minerals” written by A. C. Newman(published by John Wiley and Sons: New York in 1987). The 1:1 typestructure is a structure formed by laminating 1:1 layered structureshaving one layer of tetrahedral sheet and one layer of octahedral sheetcombined as described in the above literature “Clay Mineralogy”, and the2:1 type structure is a structure formed by laminating 2:1 layeredstructures having one layer of octahedral sheet sandwiched between twolayers of tetrahedral sheets. Examples of ion-exchange layered silicatecomprising the 1:1 layer as the main constituting layer include kaolingroup silicates such as dickite, nacrite, kaolinite, metahalloysite,halloysite or the like, and serpentine group silicates such aschrysotile, lizardite, antigorite, or the like. Examples of ion-exchangelayered silicate comprising the 2:1 layer as the main constituting layerinclude smectite group silicates, such as montmorillonite, beidellite,nontronite, saponite, hectorite, stephensite, or the like, vermiculitegroup silicates such as vermiculite or the like, mica group silicatessuch as mica, illite, sericite, glauconite, or the like, andattapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc,chlorites, and the like. Mixed layer silicates are also included. Insome embodiments, an ion-exchange layered silicate having the 2:1 typestructure is preferable. In another preferred embodiment, a smectitegroup silicate is used and in a particularly preferable example, the ionexchange layered silicate comprises montmorillonite.

Kinds of exchangeable cations (a cation contained between layers of anion-exchange layered silicate) are not specially limited, but thecations are preferably a metal of Group 1 of the Periodic Table of theElements such as sodium or potassium, a metal of Group 2 of the PeriodicTable of the Elements such as calcium or magnesium, or a transitionmetal such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium,palladium, silver, iridium, platinum, or gold, which are relativelyeasily available as industrial starting materials.

In some embodiments, the ion-exchange layered silicate has an averageparticle size of from 0.02 to 200 microns, preferably from 0.25 to 100microns, even more preferably 0.5 to 50 microns. In some embodiments,the ion exchange layered silicates have a bi-modal distribution, or evenmulti-modal distribution, of particle sizes. (Particle size, alsoreferred to as “average particle size,” “particle diameter,” or “averageparticle diameter,” is determined using a Mastersizer™ 3000 (range of 1to 3500 μm) available from Malvern Instruments, Ltd., Worcestershire,England.)

The ion exchange layered silicate may be used in a dry state and/or maybe used also in a slurry state in liquid and is preferably used as afree flowing powder after spray drying. Also, the shape of theion-exchange layered silicate is not specially limited, and the shapemay be a naturally occurring shape, an artificially synthesized shape ora shape of an ion-exchange layered silicate obtained after subjected topulverizing, granulating, and classifying.

The ion exchange layered silicates are combined with other support typecompounds, such as inorganic oxides, and used in this invention. Inanother embodiment, the ion-exchange layered silicate may be utilized aspart of an agglomerate (as described in US 2003/0096698 and U.S. Pat.No. 6,559,090, which are herein fully incorporated by reference), withat least one inorganic oxide component, such as SiO₂, Al₂O₃, MgO, AlPO₄,TiO₂, ZrO₂, or Cr₂O₃. For example, an ion exchange layered silicate,such as montmorillonite, may be combined with inorganic oxide, such assodium silicate, and then combined with the organoaluminum compound(preferably, an alkylaluminum compound).

In a preferred embodiment of the invention, the organoalumimum treatedlayered silica support is a composite in the form of agglomerates of atleast two components, namely, (A) at least one inorganic oxidecomponent, such as silica or a silicon oxide, such as sodium silicate,and (B) at least one layered silicate component, typically an ionexchange layered silicate such as those described herein, particularlymontmorillonite, particularly an ion exchange montmorillonite such asK10 or KSF. The agglomerates are an intimate admixture of Components-Aand -B.

The inorganic oxide Component-A of the agglomerate particles is derivedfrom porous inorganic oxides including SiO₂, Al₂O₃, AlPO₄, MgO, TiO₂,ZrO₂; Na₂SiO₃; and or mixed inorganic oxides including SiO₂.Al₂O₃,MgO.SiO₂Al₂O₃, SiO₂.TiO₂.Al₂O₃, SiO₂.Cr₂O₃.TiO₂ and SiO₂Cr₂O₃.TiO₂.Particularly useful inorganic oxides include Group 1 and 2 silicates,such as sodium silicate, potassium silicate, calcium silicate, magnesiumsilicate, and mixtures thereof.

Component-B of the agglomerate particles is derived from layeredsilicate materials, particularly ion-exchange layered silicates, such asthose described herein. The layered silicate derived materials inComponent-B can be amorphous or crystalline, preferably amorphous, andcan be clay or clay minerals. Preferably, the layered silicate is asmectic clay. Particularly useful ion-exchange layered silicates includemagnesia, titania, montmorillonite (EP 0 511 665 B1 and U.S. Pat. No.5,965,477), phyllosilicate, zeolites, talc, clays (U.S. Pat. No.6,034,187), and the like. The ion-exchange layered silicates can be acidtreated.

In a useful embodiment, the ion-exchange layered silicates have anacidic pH, such as less than 7, alternately from 1 to 6, alternatelyfrom 3 to 5.

The agglomerates comprising Component-A and Component-B, preferablycontain 10 to 99.5 wt %, preferably 25 to 95 wt %, preferably 90 to 99wt %, preferably 95 to 97 wt % of Component-B and 90 to 0.5 wt %,preferably 5 to 75 wt %, preferably 1 to 10 wt %, preferably 3 to 5 wt %of Component-A based upon the weight of Component-A and Component-B.

Alternately, the agglomerates comprising Component-A and Component-B,preferably contain 80 to 99.5 wt %, preferably 90 to 99 wt % ofComponent-B and preferably 20 to 0.5 wt %, preferably 10 to 1 wt % ofComponent-A based upon the weight of Component-A and Component-B.

The weight ratio of Component-A to Component-B in the agglomerate canvary typically from about 0.25:100 to about 20:100, preferably fromabout 0.5:100 to about 10:100, most preferably from about 1:100 to about5:100. The agglomerates of the present invention preferably will exhibita higher macropore content than the constituent particles as a result ofthe interparticle voids between the constituent particles. However, suchinterparticle voids may be partially or completely filled with thesmaller secondary particles in other embodiments of the spray driedagglomerates. The agglomeration of Components-A and -B may be carriedout in accordance with the methods well known to the art, in particular,by such methods as spray drying.

The agglomerates typically have an average particle size of 1 to 1000microns, preferably 50 to 500 microns, preferably 20 to 180 microns,preferably 75 to 200 microns. In some embodiments the agglomerates havea bi-modal distribution, or even multi-modal distribution, of particlesizes. Particle size, also referred to as “average particle size,”“particle diameter,” or “average particle diameter,” is determined usinga Mastersizer™ 3000 (range of 1 to 3500 pin) available from MalvernInstruments, Ltd., Worcestershire, England. Unless otherwise stated,particle size is determined at D50. D50 is the value of the particlediameter at 50% in the cumulative distribution. For example, if D50=5.8um, then 50% of the particles in the sample are equal to or larger than5.8 um and 50% are smaller than 5.8 um. (In contrast, if D90=5.8 um,then 10% of the particles in the sample are larger than 5.8 um and 90%are smaller than 5.8 um.)

The agglomerates typically have a surface area of 100 to 300 m²/g,preferably 120 to 250 m²/g, preferably 130 to 220 m²/g, alternately 100to 200 m²/g (as measured by BET).

The agglomerates typically have a pore volume of 0.1 to 0.5 cc/g,preferably 0.1 to 0.4 cc/g, preferably 0.15 to 0.35 cc/g (as measured byBET). Pore volume may be determined by the BJH method, but in event ofconflict between the results of the two methods, the BET method shall beused. The BET method shall be used for the claims to this invention.

The agglomerates typically have a spheroidal shape.

For purposes herein, the surface area (SA, also called the specificsurface area or BET surface area), pore volume (PV) of support materialsare determined by the Brunauer-Emmett-Teller (BET) method usingadsorption-desorption of nitrogen (temperature of liquid nitrogen: 77 K)with a MICROMERITICS TRISTAR II 3020 instrument after degassing of thepowders for 4 hrs. at 350° C. More information regarding the method canbe found, for example, in “Characterization of Porous Solids andPowders: Surface Area, Pore Size and Density,” S. Lowell et al.,Springer, 2004, PV refers to the total PV, including both internal andexternal PV.

For purposes herein, porosity of particles refers to the volume fractionor percentage of pore volume within a particle or body comprising askeleton or matrix of the particle material, on the basis of the overallvolume of the particle or body with respect to total volume. Theporosity and median pore diameter of particles are determined usingmercury intrusion porosimetry. Mercury intrusion porosimetry involvesplacing the sample in a penetrometer and surrounding the sample withmercury. Mercury is a non-wetting liquid to most materials and resistsentering voids, doing so only when pressure is applied. The pressure atwhich mercury enters a pore is inversely proportional to the size of theopening to the void. As mercury is forced to enter pores within thesample material, it is depleted from a capillary stem reservoirconnected to the sample cup. The incremental volume depleted after eachpressure change is determined by measuring the change in the capacity ofthe stem. This intrusion volume is recorded with the correspondingpressure.

The agglomerates are typically a free flowing powder, preferably theagglomerate is formed into free flowing particles that have apourability of 60 seconds or less as determined using ASTM 1895D. By“free flowing” is meant that the particles will flow through a funneland yield a pourability value according to ASTM 1895D; preferably, thepourability value is about 50 seconds or less, more preferably about 30seconds or less, still more preferably about 10 seconds or less, morepreferably about 5 seconds or less, still more preferably about 1 secondor less, when determined according to ASTM 1895D.

The agglomerates typically comprise from 0.1 mmol to 1 mmol aluminumthat is derived from the aluminum alkyl per gram of support. Determiningthe aluminum content derived from the aluminum alkyl is done bytitration using ¹H NMR.

Processing of a shape of an ion-exchange layered silicate bygranulating, pulverizing, or classifying may be carried out beforechemical treatment (that is, the ion-exchange layered silicate having ashape previously processed may be subjected to the chemical treatment),or an ion-exchange layered silicate may be subjected to processing of ashape after chemical treatment.

Processing may occur before or after chemical treatment with anorganoaluminum compound, an inorganic oxide and/or combination with apolymerization catalyst, however a particularly preferred methodcomprises dispersing the inorganic oxide and the ion-exchange layeredsilicate in water, thereafter spray drying, then contacting the spraydried particles with an organoaluminum compound, and thereaftercontacting with polymerization catalyst.

Examples of a granulation method used herein include a stirringgranulation method, a spraying granulation method, a tumblinggranulation method, a bricketing granulation method, a compactinggranulation method, an extruding granulation method, a fluidized layergranulation method, an emulsifying granulation method, a suspendinggranulation method a press-molding granulation method, and the like, butthe granulation method is not limited thereto. Preferable examplesinclude a stirring granulation method, a spraying granulation method, atumbling granulation method and a fluidizing granulation method, andparticularly preferable examples include a stirring granulation methodand a spraying granulation method.

When carrying out the spraying granulation method, examples of adispersion medium used for a starting slurry include water or an organicsolvent. Preferably, water is used as a dispersion medium. Aconcentration of the ion-exchange layered silicate in a startingmaterial slurry for the spraying granulation method producing sphericalparticles is from 0.1 to 70%, preferably from 1 to 50 wt %, morepreferably from 5 to 30 wt %, based upon the weight of the slurry. Anentrance temperature of hot air used in the spraying granulation methodproducing sphere particles varies depending on a dispersion medium used,but it is typically 120 to 600° C., preferably 150 to 590° C., whenwater is used as a dispersion medium. Preferably the outlet temperatureis from 80 to 260° C., preferably 100 to 200° C., preferably 120 to 180°C.

Also, in the granulation step, an organic material, an inorganicsolvent, an inorganic salt, various binders, and the like, may be used.Examples of the binders include sugar, dextrose, corn syrup, gelatin,glue, carboxymethylcelluloses, polyvinyl alcohol, water-glass, magnesiumchloride, aluminum sulfate, aluminum chloride, magnesium sulfate,alcohols, glycol, starch, casein, latex, polyethylene glycol,polyethylene oxide, tar, pitch, alumina sol, gum arabic, sodiumalginate, and the like.

Also, the pulverizing method is not specially limited, and it may beeither dry type pulverization or wet type pulverization.

When the agglomerates are formed by spray drying, they can be furthercharacterized in that typically at least 80, preferably at least 90, andmost preferably at least 95 volume % of that fraction of the supportagglomerate particles smaller that the D90 of the entire agglomerateparticle size distribution possesses microspheroidal shape (i.e.,morphology). Evaluation of the microspheroidal morphology is performedon that fraction of the particle size distribution of the supportagglomerates, which is smaller than the D90, to avoid distortion of theresults by a few large particle chunks, which because of their largevolume, would constitute a non-representative sample of the agglomeratevolume. The term “spheroidal” as used herein, means small particles of agenerally rounded, but not necessarily spherical shape. This term isintended to distinguish from irregular jagged chunks and leaf or rodlike configurations. “Spheroidal” is also intended to include polylobedconfigurations wherein the lobes are also generally rounded, althoughpolylobed structures are uncommon when the agglomerate is made asdescribed herein.

Each microspheroid is preferably composed of a loosely to densely packedcomposite of Components-A and -B typically with some, to substantiallyno, interstitial void spaces, and typically, substantially no visibleboundaries, in an electron micrograph, between particles originallyderived from Components-A and -B.

Bulk density is measured by quickly transferring (in 10 seconds) thesample powder into a graduated cylinder which overflows when exactly 100cc is reached. No further powder is added at this point. The rate ofpowder addition prevents settling within the cylinder. The weight of thepowder is divided by 100 cc to give the density.

Spray drying conditions are typically controlled in order to impart thedesired target properties described above to the agglomerate. The mostinfluential spray drying conditions are the pH of the aqueous slurry tobe spray dried, as well as its dry solids content. By “dry solidscontent” as used herein is meant the weight of solids in the slurryafter such solids have been dried at 175° C. for 3 hours, and then at955° C. for 1 hour. Thus, dry solids content is used to quantify theweight of solid ingredients which exist in the slurry and to avoidinclusion of adsorbed water in such weight.

Typically, the pH of the slurry will be controlled or adjusted to befrom about 2 to about 10 (e.g., 3 to 9, preferably from about 7 to about9, such as about 4, and the dry solids content will be controlled oradjusted to be typically from about 10 to 40, preferably from 10 to 30,preferably from about 15 to about 25, and most preferably from about 18to about 22 (e.g., 20) wt % based on the weight of the slurry and thedry weight of the gel. Control of the remaining variables in the spraydrying process, such as the viscosity and temperature of the feed,surface tension of the feed, feed rate, the selection and operation ofthe atomizer (preferably an air atomizer is employed and, optionally,with the use of a pressure nozzle, the atomization energy applied, themanner in which air and spray are contacted, and the rate of drying, arewell within the skill of the spray dry artisan once directed by thetarget properties sought to be imparted to the product produced by thespray drying. (See, for example, U.S. Pat. No. 4,131,452.)

In another embodiment, the pH of the slurry will be controlled oradjusted to be from about 3 to 7; the dry solids content will becontrolled or adjusted to be typically from about 20 to 30 wt % based onthe weight of the slurry and the dry weight of the gel; and the ratio ofComponent-A to Component-B will be in the range of 1:5 to 1:20.

In another embodiment, the pH of the slurry will be controlled oradjusted to be from about 3 to 7; the dry solids content will becontrolled or adjusted to be typically from about 20 to 30 wt % based onthe weight of the slurry and the dry weight of the gel; and the ratio ofComponent-A to Component-B will be in the range of 1:5 to 1:20 and aspray dried material having an average particle size of from 20 to 125is obtained, preferably the particle is free flowing.

Product separation from the drying air follows completion of the spraydrying stage when the dried product remains suspended in the air. Anyconvenient collection method can be employed, such as removal from thebase of the spray dryer by the use of separation equipment.

To provide uniformity to the catalyst, as well as the resulting polymer,it is desirable to calcine the support to control any residual moisturepresent in the support.

When calcination is employed, it will typically be conducted atsufficient temperature and time to reduce the total volatiles to betweenabout 0.1 and 8 wt. % where the total volatiles are determined bymeasuring the weight loss upon destructive calcination of the sample at1000° C. However, the calcination temperature will also affect theinterrelationship between the desired silica:clay ratio and theorganoaluminum compound amount, and the activity of the catalyst asdescribed hereinafter in more detail. Accordingly, calcination, whenemployed, will typically be conducted by heating the support totemperatures of typically from about 100 to about 800, preferably fromabout 150 to about 600, and most preferably from about 200 to about 300°C. for periods of typically from about 1 to about 600 (e.g., 50 to 600),and preferably from about 50 to about 300 minutes. The atmosphere ofcalcination can be air or an inert gas. Calcination should be conductedto avoid sintering.

Chemical Treatment of Ion-Exchange Layered Silicate

The chemical treatment of an ion-exchange layered silicate is carriedout by bringing it in contact with an acid, a salt, an alkali, anoxidizing agent, a reducing agent or a treating agent containing acompound intercalatable between layers of an ion-exchange layeredsilicate. The intercalation means to introduce other material betweenlayers of a layered material, and the material to be introduced iscalled a guest. Among these treatments, acid treatment or salt treatmentis particularly preferable.

A common effect achieved by chemical treatment is to exchange anintercalation cation with other cations, and in addition to this effect,the following various effects can be achieved by various chemicaltreatments. For example, acid treatment removes impurities on thesurface of silicate, and cations such as Al, Fe, Mg. or the like, in acrystal structure are eluted, thereby increasing the surface area. Thistreatment enhances the acid strength and acidity of the layeredsilicate.

Alkali treatment destroys a crystal structure of a clay mineral andchanges a structure of the clay mineral. Also, intercalation or salttreatment forms an ion composite, a molecule composite, an organicderivative, or the like, and changes a surface area or a distancebetween layers. By using an ion-exchange reaction, an exchangeableintercalated cation between layers can be replaced by other large bulkyions, thereby producing a layered material having the distance betweenlayers enlarged. Thus, the bulky ions have a function as a columnsupporting the layered structure, and are called pillars.

Examples of treating agents are illustrated below. In some embodiments,at least two kinds of members selected from the group consisting ofacids, salts, alkalis, oxidizing agents, reducing agents and compoundsintercalatable between layers of an ion-exchange layered silicate may becombined and used as treating agents. Also, acids, salts, alkalis,oxidizing agents, reducing agents and compounds intercalatable betweenlayers of an ion-exchange layered silicate may be respectively used in acombination of two or more members. Among them, a combination of a salttreatment and an acid treatment is particularly preferable.

(A) Acids

Examples of acids useful in acid treatment, include hydrochloric acid,nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid,and the like. Particularly, it is preferable to use an inorganic acid.Usually, the acid is used in the form of an acid aqueous solution. Theacid used in the treatment may be a mixture of at least two kinds ofacids. Usefully, the acid used herein is sulfuric acid.

(B) Salts

Examples of salts include salts formed from a cation selected from thegroup consisting of an organic cation, an inorganic cation and a metalion and anion selected from the group consisting of an organic anion, aninorganic anion, and a halide ion. For example, preferable examplesinclude compounds formed from a cation including at least one kind ofatom selected from Group 1 to Group 14 of the Periodic Table of theElements and at least one kind of an anion selected form an anion ofhalogen and an anion of an inorganic Bronsted acid and an organicBronsted acid. Particularly preferable examples include compounds formedfrom an anion selected from the group consisting of an anion of halogenand an anion of an inorganic Bronsted acid.

Non-limiting examples of these salts include: LiCl, LiBr, Li₂SO₄,Li₃(PO₄), LiNO₃, Li(OOCCH₃), NaCl, NaBr, Na₂SO₄, Na₃(PO₄), NaNO₃,Na(OOCCH₃), KCl, KBr, K₂SO₄, K₃(PO₄), KNO₃, K(OOCCH₃), MgCl₂, MgSO₄,Mg(NO₃)₂, CaCl₂, CaSO₄, Ca(NO₃)₂, Ca₃(C₆HSO₇)₂, Sc(OOCCH₃)₂, Sc₂(CO₃)₃,Sc₂(C₂O₄)₃, Sc(NO₃)₃, Sc₂(SO₄)₃, ScF₃, ScCl₃, ScBr₃, ScI₃, Y(OOCH₃)₃,Y(CH₃COCHCOCH₃)₃, Y₂(CO₃)₃, Y₂(C₂O₄)₃, Y(NO₃)₃, Y(ClO₄)₃, YPO₄,Y₂(SO₄)₃, YF₃, YCl₃, La(OOCH₃)₃, La(CH₃COCHCOCH₃)₃, La₂(CO₃)₃, La(NO₃)₃,La(ClO₄)₃, LaPO₄, La₂(SO₄)₃, LaF₃, LaCl₃, LaBr₃, LaI₃, Sm(OOCCH₃)₃,Sm(CH₃COCHCOCH₃)₃, Sm₂(CO₃)₃, Sm(NO₃)₃, Sm(ClO₄)₃, Sm₂(C₂O₄)₃, SmPO₄,Sm₂(SO₄)₃, SmF₃, SmCl₃, SmBr₃, SmI₃, Yb(OOCH₃)₃, Yb(NO₃)₃, Yb(C₁O₄)₃,Yb₂(C₂O₄)₃, Yb₂(SO₄)₃, YbF₃, YbCl₃, Ti(OOCCH₃)₄, Ti(CO₃)₂, Ti(NO₃)₄,Ti(SO₄)₂, TiF₄, TiCl₄, TiBr₄, TiI₄, Zr(OOCCH₃)₄, Zr(CO₃)₂, Zr(NO₃)₄,Zr(SO₄)₂, ZrF₄, ZrCl₄, ZrBr₄, ZrI₄, ZrOCl₂, ZrO(NO₃)₂, ZrO(ClO₄)₂,ZrO(SO₄), Hf(OOCCH₃)₄, Hf(CO₃)₂, Hf(NO₃)₄, Hf(SO₄)₂, HfOCl₂, HfF₄,HfCl₄, HfBr₄, HfI₄, V(CH₃COCHCOCH₃)₃, VOSO₄, VOCl₃, VCl₃, VCl₄, VBr₃,Nb(CH₃COCHCOCH₃)₅, Nb₂(CO₃)₅, Nb(NO₃)₅, Nb₂(SO₄)₅, NbF₅, NbCl₅, NbBr₅,NbI₅, Ta(OOCCH₃)₅, Ta₂(CO₃)₅, Ta(NO₃)₅, Ta₂(SO₄)₅, TaF₅, TaCl₅, TaBr₅,Ta₅, Cr(OOCCH₃)₂OH, Cr(CH₃COCHCOCH₃)₃, Cr(NO₃)₃, Cr(ClO₄)₃, CrPO₄,Cr₂(SO₄)₃, CrO₂Cl₂, CrF₃, CrCl₃, CrBr₃, CrI₃, MoOCl₄, MoCl₃, MoCl₄,MoCl₅, MoF₆, MoI₂, WCl₄, WCl₆, WF₆, WBr₅, Mn(CH₃COCHCOCH₃)₂, MnCO₃,Mn(NO₃)₂, MnO, Mn(ClO₄)₂, MnF₂, MnCl₂, MnBr₂, MnI₂, FeCO₃, Fe(NO₃)₃,Fe(ClO₄)₃, FePO₄, FeSO₄, Fe₂(SO₄)₃, FeF₃, FeCl₃, FeBr₃, FeI₃, FeC₆H₅O₇,Co(OOCCH₃)₂, Co(CH₃COCHCOCH₃)₃, CoCO₃, Co(NO₃)₂, CoC₂O₄, Co(ClO₄)₂,Co₃(PO₄)₂, CoSO₄, CoF₂, CoCl₂, CoBr₂, CoI₂, NiCO₃, Ni(NO₃)₂, NiC₂O₄,Ni(ClO₄)₂, NiSO₄, NiCl₂, NiBr₂, CuCl₂, CuBr₂, Cu(NO₃)₂, CuC₂O₄,Cu(ClO₄)₂, CuSO₄, Cu(OOCCH₃)₂, Zn(OOCCH₃)₂, Zn(CH₃COCHCOCH₃)₂, ZnCO₃,Zn(NO₃)₂, Zn(ClO₄)₂, Zn₃(PO₄)₂, ZnSO₄, ZnF₂, ZnCl₂, ZnBr₂, ZnI₂, AlF₃,AlCl₃, AlBr₃, AlI₃, Al₂(SO₄)₃, Al₂(C₂O₄)₃, Al(CH₃COCHCOCH₃)₃, Al(NO₃)₃,AlPO₄, GeCl₄, Sn(OOCCH₃)₄, Sn(SO₄)₂, SnF₄, SnCl₄, and the like.

Examples of an organic cation include an ammonium compound such astetraethylammonium, tetramethylammonium, benzyltrimethylammonium,trimethylammonium, triethylammonium, tripropylammonium,tributylammonium, dodecyl ammonium, N,N-dimethylanilinium,N,N-diethylanilinium, N,N-2,4,5-pentamethylanilinium,N,N-dimethyloctadecylammonium, octadecylammonium,N,N-dimethyl-p-n-butylanilinium, N,N-dimethyl-p-trimethylsilylanilinium,N,N-dimethyl-1-napthylanilinium, N,N-2-trimethylanilinium,2,6-dimethylanilinium, or the like, a nitrogen-containing aromaticcompound such as pyridinium, N-methylpyridinium, quinolinium,N-methylpiperidinium, 2,6-dimethylpyridinium,2,2,6,6-tetramethylpiperidinium, or the like, an oxonium compound suchas dimethyloxonium, diethyloxonium, diphenyloxonium, furanium,oxofuranium, or the like, a phosphonium compound such astriphenylphosphonium, tetraphenylphosphonium, trimesitylphosphonium, orthe like, and a phosphorus-containing aromatic compound such asphosphabenzonium, phosphanaphthalenium or the like, but the organiccation is not limited thereto.

In a preferred embodiment, the ion-exchange layered silicate has beentreated with one or more of tetraethylammonium, tetramethylammonium,benzyltrimethylammonium, trimethylammonium, triethylammonium,tripropylammonium, tributylammonium, dodecylammonium,N,N-dimethylanilinium, N,N-diethylanilinium,N,N-2,4,5-pentamethylanilinium, N,N-dimethyloctadecylammonium,octadecylammonium, N,N-dimethyl-p-n-butylanilinium,N,N-dimethyl-p-trimethylsilylanilinium, N,N-dimethyl-1-napthylanilinium,N,N-2-trimethylanilinium, 2,6-dimethylanilinium, pyridinium,quinolinium, N-methylpiperidinium, 2,6-dimethylpyridinium,2,2,6,6-tetramethylpiperidinium, dimethyloxonium, diethyloxonium,diphenyloxonium, furanium, oxofuranium, tetraphenylphosphonium,phosphabenzonium, phosphanaphthalenium, hexafluorophosphate,tetrafluoroborate, and tetraphenylborate.

In addition to the above-illustrated anions, examples of other anionsinclude an anion of a boron compound or a phosphorus compound such ashexafluorophosphate, tetrafluoroborate, tetraphenylborate, or the like,but the anion is not limited thereto.

These salts may be used alone or in a mixture of two or more. Further,they may be used in combination with acids, alkalis, oxidizing agents,reducing agents, compounds intercalatable between layers of anion-exchange layered silicate, or the like. They may be combined with atreating agent to be added to the initiation or treatment, or they maybe combined with a treating agent to be added during treatment.

(C) Alkalis

Examples of a treating agent used in alkali treatment include LiOH,NaOH, KOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, Ba(OH)₂, and the like. Since it isconsidered that the alkali treatment may damage the acidity of anion-exchanged layered silicate, it is preferable to carry out acidtreatment after achieving a structure change of a clay mineral by alkalitreatment. However, even after the alkali treatment, if an acidity andan acid amount satisfy the above mentioned ranges, the effect of thepresent invention is not damaged. Examples of a preferable compoundinclude LiOH, NaOH, KOH, Mg(OH)₂, or the like.

(D) Oxidizing Agents

Examples of an oxidizing agent include permanganates such as HMnO₄,NaMnO₄, KMnO₄ or the like, nitric acid compounds such as HNO₃, N₂O₄,N₂O, Cu(NO₃)₂, Pb(NO₃)₂, AgNO₃, KNO₃, NH₄NO₃, or the like, halogens suchas F₂, Cl₂, Br₂, or I₂, peroxides such as H₂O₂, Na₂O₂, BaO₂,(C₆H₅CO)₂O₂, K₂S₂O₈, K₂SO₅, HCO₃H, CH₃CO₃H, C₆H₅CO₃H, C₆H₄(COOH)CO₃H,CF₃CO₃H or the like, oxyacids such as MO, KClO, KBrO, KClO₃, KBrO₃,KIO₃, HIO₄, KIO₄, or the like, oxides such as CeO₂, Ag₂O, CuO, HgO,PbO₂, Bi₂O₃, OsO₄, RuO₄, SeO₂, MnO₂, As₂O₅, or the like, oxygens such asoxygen, ozone, or the like, hot concentrated sulfuric acid, a mixture offuming sulfuric acid and concentrated nitric acid, nitrobenzene, iodosocompounds, and the like.

(E) Reducing Agents

Examples of a reducing agent include hydrogen and hydrogen compoundssuch as H₂, HI, H₂S, LiAlH₄, NaBH₄, or the like, sulfur compounds suchas SO₂, Na₂S, or the like, alkali metals, alkaline earth metals, metalsof Group 3 to Group 10 of the Periodic Table of the Elements or theiralloys, metal salts of a low atomic valence state such as Fe(II),Sn(II), Ti(II), CO), or the like, CO, and the like.

(F) Intercalation Compounds

Examples of a guest compound intercalated into layers of an ion-exchangelayered silicate include a cationic inorganic compound such as TiCl₄,ZrCl₄, or the like, a metal alcoholate such as Ti(OR)₄, Zr(OR)₄,PO(OR)₃, B(OR)₃, (R is an alkyl group or an aryl group) or the like, ametal hydroxide or carboxylate ion such as [Al₁₃O₄(OH)₂₄]₇ ⁺,[Zr₄(OH)₁₄]₂ ⁺, [Fe₃O(OCOCH₃)₆]⁺, or the like, an organic compound suchas ethylene glycol, glycerol, urea, hydrazine, or the like, and anorganic cation such as an alkyl ammonium ion, or the like.

When intercalating these compounds, a polymerized material obtained byhydrolyzing a metal alcoholate such as Si(OR)₄, Al(OR)₃, Ge(OR)₄, or thelike, or a colloidal inorganic compound such as SiO₂, or the like, mayalso be present. Examples of a pillar include an oxide, or the like,formed by intercalating the above hydroxide ion between layers and thendehydrating by heat. A guest compound may be used as it is or may beused after newly adsorbing water or after heat-dehydrating. Also, theguest compound may be used alone or in a mixture of two or more of theabove solids.

The above-mentioned various treating agents may be used as a treatingagent solution by dissolving in an appropriate solvent, or it ispossible to use a treating agent itself as a solvent. Examples of ausable solvent include water, alcohols, aliphatic hydrocarbons, aromatichydrocarbons, esters, ethers, ketones, aldehydes, furans, amines,dimethylsulfoxide, dimethylformamide, carbon disulfide, nitrobenzene,pyridines, or their halides. A concentration of a treating agent in atreating agent solution is preferably from 0.1 to 100 wt %, morepreferably from 5 to 50 wt. %. If the treating agent concentration iswithin these ranges, a time required for treatment becomes shorter andan efficient production is possible.

Chemical Treatment Protocol

Acid Treatment

An acid treatment removes impurities on the surface or ion-exchanges acation present between layers, and in addition to this function, theacid treatment elutes a part or whole of cations such as Al, Fe, Mg, orthe like, in a crystal structure. Examples of acids used in acidtreatment include hydrochloric acid, nitric acid, sulfuric acid,phosphoric acid, acetic acid, oxalic acid, and the like. Particularly,it is preferable to use an inorganic acid. The acid is typically used inthe form of an acid aqueous solution. The acid used in the treatment maybe a mixture of at least two kinds of acids. Usefully, the acid usedherein is sulfuric acid.

A particular embodiment of the present invention is to carry out atreatment with an acid having a specific concentration. Anyconcentration of acid may be used, however higher acid concentrations(and higher temperatures) are more efficient. In particular using anacid concentration of more than 5 wt % (based upon the weight of theacid, any liquid diluent or solvent and the ion exchange layeredsilicate present), preferably more than 10 wt %, more preferably morethan 15 wt % has been found to be effective. In a preferred embodiment,the treatment is performed at temperatures of more than 50° C.,preferably more than 70° C., more preferably at more than 90° C. Thetreatment preferably is allowed to react for 5 minutes to 10 hours, morepreferably 30 minutes to 8 hours, more preferably 1 to 6 hours. In aparticularly preferred embodiment, the treatment occurs at 90° C. ormore for 2 to 6 hours using an acid concentration of more than 15 wt %.In another particularly preferred embodiment, the treatment occurs at100° C. or more for 2 to 4 hours using an acid concentration of morethan 15 wt %.

Generally, it is known that by subjecting the silicate to acidtreatment, impurities on the surface are removed and cations such as Al,Fe, Mg, or the like, in a crystal structure are eluted, therebyincreasing the surface area. Thus, in accordance with the progress ofacid treatment, it is considered that the surface area and a pore volumeare increased. However, in case of such concentrated acid treatment ascarried out in the present invention, a surface area value of a silicatetreated by the concentrated acid treatment employing such an acidconcentration as defined as above is rather smaller than a surface areaof a silicate treated by an acid treatment employing a lower acidconcentration to have the same substituting components eluted. This factmeans that a pore size of the silicate becomes larger. It is expectedthat this change achieves an effect of easily moving a material betweenan outer part and an inner part of a catalyst. Thus, a silicate treatedby an acid having a high concentration provides a larger pore size, andit is expected that mass transport (of a metallocene complex, a monomer,an organoaluminum compound, a heterocyclic organic compound or the like)becomes easy in the inside of a catalyst or constituting particles inthe same manner as in the outside. Accordingly, a catalyst prepared fromthe silicate of the present invention has active sites more uniformlydispersed, and it is considered that local heat generation on thecatalyst is inhibited as compared with a conventional catalyst.Particularly, when producing an easily meltable or soluble polymer,e.g., in a case of low melting point random polymerization of apropylene type monomer, it is possible to carry out polymerization at ahigh activity and in a state of maintaining dispersed particles, whichcould not be conventionally achieved. After appropriate acid treatmentthe ion-exchange layered silicate will, preferably, have a surface areain the range of 100 to 450 m²/g, preferably 150 to 400 m²/g, morepreferably 200 to 350 m²/g.

An acid used for the concentrated acid treatment may be the same asthose used in an ordinary acid treatment, but is preferably sulfuricacid, nitric acid or hydrochloric acid more preferably sulfuric acid.

Salt Treatment

Further, in the present invention, one may carry out a salt treatment.The salt treatment means a treatment carried out for the purpose ofexchanging cations in an ion-exchange layered silicate. The treatingconditions with a salt are not specially limited, but it is preferableto carry out the salt treatment under conditions of a salt concentrationof from 0.1 to 50 wt %, a treating temperature of from room temperatureto a boiling point and a treating time of from 5 minutes to 24 hours insuch a manner as to elute at least a part of the materials constitutingan ion-exchange layered silicate. Also, the salt may be used in anorganic solvent such as toluene, n-heptane, ethanol, or the like, or maybe used in the absence of a solvent if it is liquid-like at the treatingtemperature, but it is, preferably, used as an aqueous solution.However, depending on a kind of a salt employed, the salt treatmentachieves an effect similar to an acid treatment.

In the present invention, it is preferable to ion exchange at least 40%,preferably at least 60% of ion exchangeable cations of Group 1 metalscontained in an ion-exchange layered silicate with cations dissociatedfrom the salts as described above. After carrying out the above chemicaltreatment, it is preferable to remove ions eluted from the treatment andan excess amount of a treating agent. For this operation, water or anorganic solvent is generally used. After dehydrating, drying is carriedout generally at a drying temperature of from 100 to 800° C., preferablyfrom 150 to 600° C.

Drying of Chemically Treated Ion-Exchange Layered Silicate

These ion-exchange layered silicates change their properties dependingon a drying temperature employed even when their structures are notdestroyed, and it is, therefore, preferable to change a dryingtemperature depending on their uses. The drying period is usually in arange of from 1 minute to 24 hours, preferably from 5 minutes to 6hours, and a drying atmosphere is preferably dry air, dry nitrogen, dryargon, or carried out under reduced pressure. A drying method is notspecially limited, but various methods may be employed.

In a preferred embodiment, ion-exchange layered silicates subjected toboth acid and/or salt (or a combination thereof) chemical treatmentsdescribed above, have one or more of the following features (as outlinedin U.S. Pat. No. 6,531,552 B2 and US 2003/0027950 A1), which is fullyincorporated herein by reference):

(1) an amount of acid sites having a pKa of −8.2 or less of 0.05 mmol/g(where the amount is equivalent to the mmol/g of 2,6-dimethylpyridineconsumed for neutralization),

(2) performance that in desorption isotherm by nitrogenadsorption-desorption method, a ratio of a remaining adsorption amount(b) at a relative pressure P/Po=0.85 to an adsorption amount (a) at arelative pressure P/Po=1 satisfies the formula, (b)/(a)≥0.8,(3) performance that in adsorption isotherm and desorption isotherm bynitrogen adsorption-desorption method, a difference between a remainingadsorption amount (b) at a relative pressure P/Po=0.85 and an adsorptionamount (c) in adsorption isotherm at a relative pressure P/Po=0.85satisfies the formula, (b)−(c)>25 (cc/g),(4) a pore size distribution curve calculated from the desorptionisotherm by nitrogen adsorption-desorption method, a pore diameter D_(m)showing a maximum peak intensity D_(VM) from 60 to 200 Å,(5) in a pore size distribution curve calculated from desorptionisotherm by nitrogen adsorption-desorption method, a pore diameterD_(m1/2) (Å) on the smaller pore size side corresponding to a ½ peakintensity of the maximum peak intensity D_(VM) has a relation ofD_(m1/2)/D_(m) of at least 0.65 and less than 1, provided that thelargest value is employed when there are a plurality of D_(m1/2) values,and or(6) an average crushing strength of at least 3 MPa as measured by aminute compression tester.(1) Acid Strength/Acid Site Density

The term “acid” used herein is one category classifying a material, andis defined as a material of Bronsted acid or Lewis acid. Also, the term“acid site” is defined as a constituting unit of a material exhibiting aproperty as an acid, and for the present invention, its amount isanalyzed by the method described in U.S. Pat. No. 6,531,552 B2, which isfully incorporated herein by reference. When a chemically treatedion-exchange layered silicate is used as the support or carrier, theamount of a specific acidity is measured with regard to a silicateobtained after the chemical treatment.

In one embodiment, the ion-exchange layered silicate is acidic in natureas determined by titration methods as outlined in U.S. Pat. No.6,531,552 B2, which is fully incorporated herein by reference.

In another embodiment, it is important to control an acidity and amountof acid sites, so as to afford an ion-exchange layered silicate thatcontains aluminum in an atomic ratio of Al/Si in a range of from 0.05 to0.4, preferably from 0.05 to 0.25, more preferably from 0.07 to 0.23.The Al/Si atomic ratio is regarded as an index of acid treatment of theclay constituent. Furthermore, the chemically treated ion-exchangelayered silicate having an acid site of at most −8.2 pKa, with theamount of acid site being equivalent to at least 0.05 mmol/g of2,6-dimethylpyridine consumed for neutralization (as described in U.S.Pat. No. 6,531,552 B2). In general, the preferred amount of acid sitespresent in the ion-exchange layered silicate is 0.05 mmol/g or more andthe amount of acid sites is preferably as high as possible.

(2) Performance in Nitrogen Adsorption/Desorption Isotherm

In the present invention, measurement of the adsorption and desorptionisotherm by the nitrogen adsorption-desorption method are carried out inaccordance with the Brunauer-Emmett-Teller (BET) method usingadsorption-desorption of nitrogen (temperature of liquid nitrogen, 77 K)with a MICROMERITICS TRISTAR II 3020 instrument after degassing of thepowders for 4 hrs at 350° C. More information regarding the method canbe found, for example, in “Characterization of Porous Solids andPowders: Surface Area, Pore Size and Density”, S. Lowell et al.,Springer, 2004.

In general, the nitrogen adsorption-desorption isotherms forion-exchange layered silicates exhibit an adsorption hysteresis.Detailed descriptions of adsorption-desorption fundamentals, includinghysteresis, are discussed in “Adsorption Technology and Design” byCrittenden and Thomas and is incorporated by reference.

In one embodiment, the chemically treated ion-exchange layered silicateperformance in the nitrogen adsorption-desorption isotherm exhibits ahysteresis.

In a preferred embodiment, the ion-exchange layered silicate exhibitsthe following performance in the nitrogen adsorption-desorptionisotherm: that in desorption isotherm by the nitrogenadsorption-desorption method, a ratio of a remaining adsorption amount(b) at a relative pressure P/Po=0.85 to an adsorption amount (a) at arelative pressure P/Po=1 satisfies the formula, (b)/(a)≥0.8, (3)performance that in adsorption isotherm and desorption isotherm bynitrogen adsorption-desorption method, a difference between a remainingadsorption amount (b) at a relative pressure P/Po=0.85 and an adsorptionamount (c) in adsorption isotherm at a relative pressure P/Po=0.85satisfies the formula, (b)−(c)>25 (cc/g).

Examples of the analyzing apparatus include commercially availableproducts such as Autosorb of Quantachrome Company or Omnisorp of CoulterInc., or the like.

(3) Pore Size Distribution

The evaluation of the pore size distribution in the present inventionemploys the desorption isotherm. The desorption isotherm is a curveobtained while reducing the relative pressure. The desorption isothermshows a lower relative pressure to the same desorbed gas amount ascompared with adsorption isotherm, and, consequently, shows a lower freeenergy state, and is generally considered to be closer to a state ofreal thermodynamic stability.

In one embodiment, an ion-exchange layered silicate with any pore sizeand or any pore size distribution may be used.

In another embodiment, included in this invention is the preferred poresize distributions of the ion-exchange layered silicate as described inUS 2003/0027950 A1 (which is fully incorporated herein by reference) andlisted above in “features” 4 and 5. Where D_(m) (from differentialvalues of pore volumes) represents a pore size diameter showing amaximum peak intensity and is generally expressed as “most frequentlyappearing pore diameter”, D_(VM) represents a maximum peak intensity andD_(m1/2) represents a pore size diameter on the smaller diameter sidecorresponding to a point, the peak intensity of which is ½ of themaximum peak intensity. A pore diameter D_(m1/2) is present, at leastone respectively, on both sides of D_(m), i.e., on the larger diameterside of D_(m) and on the smaller diameter side of D_(m), but a value onthe smaller diameter side is taken as the D_(m1/2) value in the presentinvention. Also, if there are a plurality of D_(m1/2) values on thesmaller diameter side, the largest value is employed for calculation. Inone embodiment, the D_(m1/2)/D_(m) can range from 0.1 to 0.9. In anotherembodiment, a D_(m1/2)/D_(m) value is preferably at least 0.68, morepreferably at least 0.70. Furthermore, a pore size distribution curvecalculated from desorption isotherm by the nitrogenadsorption-desorption method, a pore diameter D_(m1/3) (Å) on thesmaller pore size side corresponding to a ⅓ peak intensity of themaximum peak intensity D_(vm) has a relation of D_(m1/3)/D_(m) of atleast 0.55 and less than 1, provided that the largest value is employedwhen there are a plurality of D_(m1/3) values. In an analogous manner asD_(m1/2), a pore diameter D_(m1/3) value is present respectively on bothsides of D_(m), i.e., at least one on the larger diameter side of D_(m)and at least one on the smaller diameter side of D, but a value on thesmaller diameter side is defined as D_(m1/3). Also, when there are aplurality of D_(m1/3) values on the smaller diameter side, the largestvalue is employed for calculation. A D_(m1/3)/D_(m) value is,preferably, at least 0.56, more preferably at least 0.57. If theD_(m1/3)/D_(m) value is less than 0.56, a considerable amount of smallerdiameter pores are present, which is not preferred.

Moreover, the pore size distribution calculated for desorption isothermby the nitrogen adsorption-desorption method is a substantially unimodalpeak. That is, there is not present a second peak, and if it is present,its intensity is at most 50%, preferably at most 40%, particularly atmost 30% of a maximum peak intensity D_(VM).

Also, the pore size distribution curve calculated from desorptionisotherm by the nitrogen adsorption-desorption method, wherein a peakintensity at a pore diameter of 50 Å is defined as D_(V50A),D_(V50A)/D_(VM) is at least 0.01 and at most 0.40, preferably at least0.03 and at most 0.38, more preferably at least 0.05 and at most 0.36.If the D_(V50A)/D_(VM) value exceeds 0.38, a considerable amount ofsmaller diameter pores are contained.

Thus, an ion-exchange layered silicate may have a predetermined poresize, but its pore size is sufficiently large to accept a metallocenecomplex, an activator, an organoaluminum compound, and a monomer.Accordingly, these compounds participating in the reaction easily enterinto pores in respective stages of formation of a catalyst, activation,prepolymerization and polymerization, and complexes are highly dispersedin carriers, and consequently metallocene catalyst active sites arethought to be uniformly formed. In a preferred embodiment, the ionexchange layered silicate has a pore size that is sufficiently largeenough that the catalyst compound, the organoaluminum and activatorcompounds may freely enter and diffuse evenly within the particle.Preferred pore sizes include 40 Angstroms to 500 Angstroms, preferably50 Angstroms to 300 Angstroms, more preferably 70 to 200 Angstroms.

(4) Carrier Strength

In one embodiment, the spray dried agglomerate has a compressionfracture strength (also called average crushing strength) as measured bya minute compression tester. Preferably, the ion exchange layeredsilicate has a compression fracture strength of 3 to 20 MPa. Preferably,the average crushing strength is at least 5 MPa, more preferably atleast 7 MPa. In addition, the upper limit of the ion-exchange layeredsilicate strength is, preferably, an average crushing strength of atmost 20 MPa, more preferably at most 18 MPa.

Organoaluminum Compound

In the present invention ion-exchange layered silicate is preferablycontacted with an organoaluminum compound, optionally, before treatmentwith the catalyst compound(s).

In one embodiment, preferred organoaluminum compounds described aboveare represented by the Formula:AlR₃  (Formula I)wherein each R is independently a substituted or unsubstituted alkylgroup and/or a substituted or unsubstituted aryl group. Preferably R isan alkyl group containing 1 to 30 carbon atoms. Preferred R groupsinclude methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, docecyl, aryl, and all isomers thereof.

In another embodiment, the preferred organoaluminum compounds includealkylaluminum compounds and/or alumoxanes, preferably methylalumoxane,modified methylalumoxane, or ethylalumoxane. The organoaluminumcompounds include alkylaluminum compounds where the alkyl is a C1 to C40linear, branched or cyclic alkyl, preferably a C1 to C12 linear orbranched alkyl, preferably methyl, ethyl, propyl, butyl, isobutyl,n-butyl, isopentyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl ordodecyl, even more preferably methyl, ethyl, propyl, butyl, isobutyl,n-butyl, or hexyl. Preferred organoaluminum compounds include thoserepresented by the Formula:AlR_(n)Y_(3-n)  (Formula II)wherein R is a hydrocarbon group having a carbon number of from 1 to 30,preferably 4 to 12, Y is hydrogen, halogen, an alkoxy group or a siloxygroup, and n is 1, 2, or 3. Particularly preferred alkyl aluminumcompounds useful in this invention include: trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, tri-iso-octylaluminum, triphenylaluminum, andcombinations thereof.

In another embodiment, the organoaluminum compounds also includecombinations of organoaluminum compounds. For example, it is possible touse a mixture of organoaluminum compounds such as two or more oftrimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, tri-iso-octylaluminum, andtriphenylaluminum.

In another embodiment, the organoaluminum compound comprises one or morealumoxanes, which are generally oligomeric compounds, containing—Al(R)—O— or —Al(R)₂—O— subunits, where R is an alkyl group, preferablya C1 to C40 linear, branched or cyclic alkyl, preferably a C1 to C12linear or branched alkyl, preferably methyl, ethyl, propyl, butyl,isobutyl, n-butyl, isopentyl, pentyl, hexyl, heptyl octyl, nonyl, decylor dodecyl, even more preferably methyl, ethyl, propyl, butyl, isobutyl,n-butyl, or hexyl. Examples of alumoxanes include methylalumoxane (MAO),modified methylalumoxane (MMAO), ethylalumoxane, isobutylalumoxane,tetraethyldialumoxane and di-isobutylalumoxane. Alumoxanes may beproduced by the hydrolysis of the respective trialkylaluminum compound.MMAO may be produced by the hydrolysis of trimethylaluminum and a highertrialkylaluminum such as triisobutylaluminum. There are a variety ofmethods for preparing alumoxane and modified alumoxanes, non-limitingexamples of which are described in U.S. Pat. Nos. 4,665,208; 4,952,540;5,091,352; 5,206,199; 5,204,419; 4,874,734; 4,924,018; 4,908,463;4,968,827; 5,308,815; 5,329,032; 5,248,801; 5,235,081; 5,157,137;5,103,031; 5,391,793; 5,391,529; 5,693,838; 5,731,253; 5,731,451;5,744,656; 5,847,177; 5,854,166; 5,856,256; 5,939,346; EP 561 476; EP279 586; EP 594 218; EP 586 665; WO 94/10180; and WO 99/15534; all ofwhich are fully incorporated herein by reference.

Contact between an ion-exchange layered silicate and an organoaluminumcompound can be carried out under an inert gas atmosphere such asnitrogen in a solvent of an inert hydrocarbon such as hexane, heptane,pentane, cyclohexane, benzene, toluene, xylene, or the like, and thesolvent may be used alone or in a mixture of two or more.

An amount of an organoaluminum compound used is preferably from 0.01 to1000 mmol, more preferably from 0.1 to 100 mmol, per 1 g of anion-exchange layered silicate.

A concentration of an ion-exchange layered silicate in a solvent ispreferably from 0.001 to 100 g/mL, more preferably form 0.01 to 10 g/mL,and a concentration of an organoaluminum compound is preferably from0.001 to 100 mmol/mL, more preferably from 0.01 to 10 mmol.

Contacting may be carried out by dispersing an ion-exchange layeredsilicate in a solvent and then bringing an organoaluminum compound incontact therewith. Alternatively, contacting may be carried out byadding an organoaluminum compound to a solvent and then dispersing anion-exchange layered silicate therein.

The contacting treatment is carried out generally at a temperature offrom −50° C. to a boiling point of a solvent, preferably from 0° C. to aboiling point of a solvent. The contacting time is from 1 minute to 48hours, preferably from 1 minute to 24 hours.

The order of contacting an organoaluminum compound with an ion-exchangelayered silicate is not specially limited as far as the object of thepresent invention is achieved, but it is more effective to carry out thecontacting treatment after chemical treatment of the silicate orpreferably after drying carried out after the chemical treatment. It isalso preferable to contact the organoaluminum compound with anion-exchange layered silicate after spray drying the aqueous mixture ofion-exchange layered silicate and inorganic oxide.

Also, the order of contacting treatment step of an organoaluminumcompound and an ion-exchange layered silicate and the granulation stepof an ion-exchange layered silicate is not specially limited as far asthe object of the present invention is achieved, but it is preferable tocarry out the treatment with an organoaluminum compound aftergranulating the silicate.

Further, it is possible to enhance the effect of the present inventionby combining the above-mentioned respective treatments. Thus, aftercontrolling a particle size distribution and a carrier particle strengthby granulating an ion-exchange layered silicate, a carrier obtainedthrough the following Step 1 and Step 2 is used as a catalyst componentfor olefin polymerization.

Step 1: after granulating an ion-exchange layered silicate, the silicateis treated with an acid having an acid concentration as described aboveand is then contacted with an inorganic oxide and thereafter spraydried.

Step 2: after carrying out step 1, the silicate-inorganic oxide particleis treated with an organoaluminum compound, which is any organoaluminumcompound from the discussion above.

Preferred treated organoaluminum layered silicates include:triethyaluminum treated montmorillonite, triisobutylaluminum treatedmontmorillonite, triethylaluminum treated montmorillonite/silicate,preferably where the montmorillonite/silicate is spray dried,tri-n-octylaluminum treated monmorillonite-silicate, preferably wherethe montmorillonite/silicate is spray dried, trimethylaluminum treatedmontmorillonite-silicate, preferably where the montmorillonite/silicateis spray dried, and the like.

Activators

The term “activator” is used herein to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral catalyst compound to a catalytically active metallocenecompound cation. The organoaluminum treated layered silicates alone orin combination with inorganic oxides described herein function as anactivator and thus allow polymerization without the use of traditionalactivators such as alumoxanes or non-coordinating anions. Whiletraditional activators can also be used, it is useful if traditionalactivators are not present or if present are present at a ratio ofactivator metal (such as Al or B) to catalyst transition metal of lessthan 1:1, preferably less than 0.5 to 1, preferably less than 0.1:1.

Alumoxanes

Alumoxanes are generally oligomeric compounds containing —Al(R1)-O—sub-units, where R1 is an alkyl group. Examples of alumoxanes includemethylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane,isobutylalumoxane, and mixtures thereof. Alkylalumoxanes and modifiedalkylalumoxanes are suitable as catalyst activators, particularly whenthe abstractable ligand is an alkyl, halide, alkoxide, or amide.Mixtures of different alumoxanes and modified alumoxanes may also beused. It may be preferable to use a visually clear methylalumoxane. Acloudy or gelled alumoxane can be filtered to produce a clear solutionor clear alumoxane can be decanted from the cloudy solution. Anotheruseful alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A(commercially available from Akzo Chemicals, Inc. under the trade nameModified Methylalumoxane type 3A, covered under U.S. Pat. No.5,041,584). In preferred embodiments of this invention, the activator isan alkylalumoxane, preferably methylalumoxane or isobutylalumoxane.

Preferably alumoxane is not present, or if present is present at analuminum to transition metal ratio of less than 10:1, preferably 1:0,preferably less than 0.1:1.

Stoichiometric Activators

In alternate embodiments, the catalyst system of this invention furthercomprises one or more stoichiometric activators. A stoichiometricactivator is a non-alumoxane compound which when combined in a reactionwith the metallocene compound forms a catalytically active species at amolar ratio of stoichiometric activator to metallocene compound of 10:1or less (preferably 5:1, more preferably 2:1, or even more preferably1:1), such as a compound comprising a non-coordinating anion.Preferably, a stoichiometric activator is not present, or if present ispresent at a molar ratio of stoichiometric activator to catalystcompound of less than less than 1:1, preferably 0.1:1, preferably lessthan 0.01:1.

Stoichiometric activators may comprise an anion, preferably anon-coordinating anion. The term “non-coordinating anion” (NCA) means ananion which either does not coordinate to said cation or which is onlyweakly coordinated to said cation thereby remaining sufficiently labileto be displaced by a neutral Lewis base. “Compatible” non-coordinatinganions are those which are not degraded to neutrality when the initiallyformed complex decomposes. Further, the anion will not transfer ananionic substituent or fragment to the cation so as to cause it to forma neutral four coordinate metallocene compound and a neutral by-productfrom the anion. Non-coordinating anions useful in accordance with thisinvention are those that are compatible, stabilize the metallocenecation in the sense of balancing its ionic charge at +1, yet retainsufficient lability to permit displacement by an ethylenically oracetylenically unsaturated monomer during polymerization.

The ionic stoichiometric activators are represented by the followingFormula (1):(Z)_(d) ⁺ A ^(d−)  (1)wherein (Z)_(d) ⁺ is the cation component and A^(d−) is the anioncomponent; where Z is (L-H) or a reducible Lewis Acid, L is a neutralLewis base; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is anon-coordinating anion having the charge ^(d−); and d is an integer from1 to 3.

When Z is (L-H) such that the cation component is (L-H)_(d) ⁺, thecation component may include Bronsted acids such as protonated Lewisbases capable of protonating a moiety, such as an alkyl or aryl, fromthe bulky ligand metallocene-containing transition metal catalystprecursor, resulting in a cationic transition metal species. Preferably,the activating cation (L-H)_(d) ⁺ is a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such asdimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

When Z is a reducible Lewis acid, (Z)_(d) ⁺ is preferably represented bythe formula: (Ar3C)⁺, where Ar is aryl or aryl substituted with aheteroatom, a C1 to C40 hydrocarbyl, or a substituted C1 to C40hydrocarbyl, preferably (Z)_(d) ⁺ is represented by the formula:(Ph3C)⁺, where Ph is phenyl or phenyl substituted with a heteroatom, aC1 to C40 hydrocarbyl, or a substituted C1 to C40 hydrocarbyl. In apreferred embodiment, the reducible Lewis acid is triphenyl carbenium.

The anion component A^(d−) includes those having the formula[M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6,preferably 3, 4, 5, or 6; (n−k)=d; M is an element selected from group13 of the Periodic Table of the Elements, preferably boron or aluminum;and each Q is, independently, a hydride, bridged or unbridgeddialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, andhalosubstituted-hydrocarbyl radicals, said Q having up to 20 carbonatoms with the proviso that in not more than one occurrence is Q ahalide, and two Q groups may form a ring structure. Preferably, each Qis a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, morepreferably each Q is a fluorinated aryl group, and most preferably eachQ is a pentafluoryl aryl group. Examples of suitable A^(d−) componentsalso include diboron compounds as disclosed in U.S. Pat. No. 5,447,895,which is fully incorporated herein by reference.

In other embodiments of this invention, the ionic stoichiometricactivator may be an activator comprising expanded anions, represented bythe Formula:(A* ^(+a))_(b)(Z*J* _(j))^(−c) _(d);

-   -   wherein A* is a cation having charge +a; Z* is an anion group of        from 1 to 50 atoms not counting hydrogen atoms, further        containing two or more Lewis base sites; J* independently each        occurrence is a Lewis acid coordinated to at least one Lewis        base site of Z*, and, optionally, two or more such J* groups may        be joined together in a moiety having multiple Lewis acid        functionality; J is a number from 2 to 12; and a, b, c, and d        are integers from 1 to 3, with the proviso that a×b is equal to        c×d. Examples of such activators comprising expandable anions        may be found in U.S. Pat. No. 6,395,671, which is fully        incorporated herein by reference.        Optional Co-Catalysts

In addition to the organoaluminum treated layered silicates,co-catalysts may be used. Aluminum alkyl or organometallic compoundswhich may be utilized as co-catalysts (or scavengers) include, forexample, triethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diethyl aluminum chloride, dibutyl zinc, diethylzinc, and the like.

Preferably, cocatalyst is present at a molar ratio of co-catalyst metalto transition metal of less than 100:1, preferably less than 50:1,preferably less than 15:1, preferably less than 10:1. In alternateembodiments, the cocatalyst is present at 0 wt %.

Other additives may also be used, as desired, such as one or morescavengers, promoters, modifiers, reducing agents, oxidizing agents,aluminum alkyls, or silanes.

Methods of Making the Catalyst System

Any method of combining the catalyst compound and support may be used.In some embodiments of this invention, the support material is slurriedin a non-polar solvent and the resulting slurry is contacted with asolution of a catalyst. The slurry mixture may be heated to 0° C. to 70°C., preferably to 25° C. to 60° C., preferably at room temperature (25°C.). Contact times typically range from 0.5 hour to 24 hours, from 2hours to 16 hours, or from 4 hours to 8 hours.

Suitable non-polar solvents are materials in which all of the reagentsused herein, i.e., the activator, and the catalyst compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, alone or in combination, may alsobe employed.

The volatiles are removed to yield the supported catalyst system,preferably as a free-flowing solid.

In some embodiments, the weight ratio of the catalyst to the solidsupport material may be from 10:1 to 0.0001:1, from 1:1 to 0.001:1, orfrom 0.1:1 to 0.001:1. The weight ratio of the support material to theactivator compound (such as an alumoxane) may range from 1:10 to 100:1,from 1:1 to 100:1, or from 1:1 to 10:1.

In some embodiments, the supported catalyst system is suspended in aparaffinic agent, such as mineral oil, for easy addition to a reactorsystem, for example a gas phase polymerization system.

Polymerization Processes

This invention also relates to polymerization processes comprising:contacting one or more olefins with the catalyst system of the presentinvention under polymerization conditions; and obtaining an olefinpolymer.

The catalyst systems described herein are useful in the polymerizationof all types of olefins. This includes polymerization processes whichproduce homopolymers, copolymers, terpolymers, and the like, as well asblock copolymers and impact copolymers.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀olefins, preferably C₂ to C₂₀ olefins, preferably C₂ to C₁₂ olefins,preferably ethylene, propylene, butene, pentene, hexene, heptene,octene, nonene, decene, undecene, dodecene, and isomers thereof,preferably alpha olefins. In a preferred embodiment of the invention,the monomer comprises propylene and optional comonomers comprising oneor more ethylene or C₄ to C₄₀ olefins, preferably C₄ to C₂₀ olefins, orpreferably C₆ to C₁₂ olefins. The C₄ to C₄₀ olefin monomers may belinear, branched, or cyclic. The C₄ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups. In anotherpreferred embodiment, the monomer comprises ethylene and optionalcomonomers comprising one or more C₃ to C₄₀ olefins, preferably C₄ toC₂₀ olefins, or preferably C₆ to C₁₂ olefins. The C₃ to C₄₀ olefinmonomers may be linear, branched, or cyclic. The C₃ to C₄₀ cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include heteroatoms and/or one or more functional groups.

Examples of C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, preferably hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, preferablynorbornene, norbornadiene, and dicyclopentadiene. Preferably, thepolymerization or co-polymerization is carried out using olefins such asethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and1-octene, vinylcyclohexane, norbornene, and norbornadiene. Inparticular, propylene and ethylene are polymerized.

In some embodiments, where butene is the comonomer, the butene sourcemay be a mixed butene stream comprising various isomers of butene. The1-butene monomers are expected to be preferentially consumed by thepolymerization process. Use of such mixed butene streams will provide aneconomic benefit, as these mixed streams are often waste streams fromrefining processes, for example, C₄ raffinate streams, and can thereforebe substantially less expensive than pure 1-butene.

Polymerization processes of this invention can be carried out in anymanner known in the art, in slurry, in suspension or in the gas phase,continuously or batchwise, or any combination thereof, in one or moresteps. Slurry, and gas phase processes are preferred. A bulk homogeneousprocess is also useful. (A bulk process is defined to be a process wheremonomer concentration in all feeds to the reactor is 70 vol % or more.)Alternately, no solvent or diluent is present or added in the reactionmedium (except for the small amounts used as the carrier for thecatalyst system or other additives, or amounts typically found with themonomer; e.g., propane in propylene). In another embodiment, the processis a slurry process. As used herein the term “slurry polymerizationprocess” means a polymerization process where a supported catalyst isemployed and monomers are polymerized on the supported catalystparticles and at least 95 wt % of polymer products derived from thesupported catalyst are in granular form as solid particles (notdissolved in the diluent).

Gas Phase Polymerization

Generally, in a fluidized gas bed process used for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream is withdrawn from the fluidized bed andrecycled back into the reactor. Simultaneously, polymer product iswithdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See for example U.S. Pat. No. 4,543,399; U.S. Pat.No. 4,588,790; U.S. Pat. No. 5,028,670; U.S. Pat. No. 5,317,036; U.S.Pat. No. 5,352,749; U.S. Pat. No. 5,405,922; U.S. Pat. No. 5,436,304;U.S. Pat. No. 5,453,471; U.S. Pat. No. 5,462,999; U.S. Pat. No.5,616,661; and U.S. Pat. No. 5,668,228; all of which are fullyincorporated herein by reference.)

In an embodiment of the invention, any catalyst/support combinationdescribed herein is used in the gas phase to produce olefin polymer,preferably an ethylene polymer.

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers along with catalyst are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

In an embodiment, a preferred polymerization technique useful in theinvention is referred to as a particle form polymerization, or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is well known in the art, anddescribed in, for instance, U.S. Pat. No. 3,248,179; which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is fully incorporated herein byreference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst, as a slurry in isobutane or as a dry freeflowing powder, is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. (In oneembodiment 500 ppm or less of hydrogen is added, or 400 ppm or less or300 ppm or less. In other embodiments at least 50 ppm of hydrogen isadded, or 100 ppm or more, or 150 ppm or more.)

The reactor may be maintained at a pressure of 3620 kPa to 4309 kPa andat a temperature in the range of about 60° C. to about 104° C. dependingon the desired polymer melting characteristics. Reaction heat is removedthrough the loop wall since much of the reactor is in the form of adouble jacketed pipe. The slurry is allowed to exit the reactor atregular intervals or continuously to a heated low pressure flash vessel,rotary dryer and a nitrogen purge column in sequence for removal of theisobutane diluent and all unreacted monomer and comonomers. Theresulting hydrocarbon free powder is then compounded for use in variousapplications.

Other additives may also be used in the polymerization, as desired, suchas one or more scavengers, promoters, modifiers, chain transfer agents(such as diethyl zinc), reducing agents, oxidizing agents, hydrogen,aluminum alkyls, or silanes.

Useful chain transfer agents are typically alkylalumoxanes, a compoundrepresented by the formula AlR₃, ZnR₂ (where each R is, independently, aC₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl, butyl, penyl,hexyl, heptyl, octyl, or an isomer thereof) or a combination thereof,such as diethyl zinc, methylalumoxane, trimethylaluminum,triisobutylaluminum, trioctylaluminum, or a combination thereof.

Preferred polymerizations can be run at any temperature and/or pressuresuitable to obtain the desired polymers. Typical temperatures and/orpressures include a temperature greater than 30° C., preferably greaterthan 50° C., preferably greater than 65° C., alternately less than 200°C., preferably less than 150° C., most preferably less than 140° C., andat a pressure in the range of from 0.35 MPa to 10 MPa, preferably from0.45 MPa to 6 MPa, or preferably from 0.5 MPa to 4 MPa.

In a typical polymerization, the run time of the reaction is up to 300minutes, preferably in the range of from 5 to 250 minutes, or preferablyfrom 10 to 120 minutes.

If necessary, hydrogen is added as a molecular-weight regulator and/orin order to increase the activity. The overall pressure in thepolymerization system usually is at least 0.5 bar, preferably at least 2bar, most preferred at least 5 bar. Pressures higher than 100 bar, e.g.,higher than 80 bar and, in particular, higher than 64 bar, are usuallynot preferred. In some embodiments, hydrogen is present in thepolymerization reactor at a partial pressure of from 0.001 to 100 psig(0.007 to 690 kPa), preferably from 0.001 to 50 psig (0.007 to 345 kPa),preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1to 10 psig (0.7 to 70 kPa).

In an alternate embodiment, the productivity of the catalyst is at least50 gpolymer/g (cat)/hour, preferably 500 or more gpolymer/g (cat)/hour,preferably 5000 or more gpolymer/g (cat)/hour, preferably 50,000 or moregpolymer/g (cat)/hour.

In an alternate embodiment, the conversion of olefin monomer is at least10%, based upon polymer yield and the weight of the monomer entering thereaction zone, preferably 20% or more, preferably 30% or more,preferably 50% or more, preferably 80% or more. A “reaction zone”, alsoreferred to as a “polymerization zone”, is a vessel where polymerizationtakes place, for example, a batch reactor. When multiple reactors areused in either series or parallel configuration, each reactor isconsidered as a separate polymerization zone. For a multi-stagepolymerization in both a batch reactor and a continuous reactor, eachpolymerization stage is considered as a separate polymerization zone. Inpreferred embodiments, the polymerization occurs in one, two, three,four, or more reaction zones.

In a preferred embodiment, the catalyst system used in thepolymerization comprises no more than one catalyst compound.

Other additives may also be used in the polymerization, as desired, suchas one or more scavengers, promoters, modifiers, chain transfer agents(such as diethyl zinc), reducing agents, oxidizing agents, hydrogen,aluminum alkyls, or silanes.

Polyolefin Products

This invention also relates to polyolefins produced using the supportedcatalyst systems of this invention, particularly propylene and ethylenehomopolymers and copolymers. In some embodiments, the invention relatesto polyolefins produced using the catalyst systems of this invention,particularly polyethylene, having a density in the range of 0.916 to0.955 g/cc, preferably in the range of from 0.920 to 0.950 g/cc,preferably 0.920 to 0.940 g/cc, preferably 0.920 to 0.935 g/cc.

In an embodiment of the invention, the process described herein producesa polyolefin composition “A”, which has an Mw of 1,000,000 g/mol ormore, and comprises less than 5 wt %, alternately from 0.01 to 5 wt %alternately 0.1 to 5 wt %, alternately 0.25 to 3 wt % or less,alternately 0.5 to 1 wt %) of the layered silicate (which may or may notbe in contact with the organoaluminum compound or the inorganic oxide),based upon the weight of the polyolefin and the layered silicate, wherepolyolefin composition A has: 1) no diffraction peak resulting frominterlamellar spacing of the organoaluminum treated layered silicate,and/or 2) a diffraction peak resulting from interlamellar spacing of theorganoaluminum treated layered silicate of Z Angstroms or more, whereZ=5X (alternately Z=10X, alternately Z=15X, alternately Z=20X), where Xis the diffraction peak resulting from interlamellar spacing of thelayered silicate used in the support before combination with thecatalyst compound, as measured by wide angle x-ray scattering (WAXS).

SAXS/MAXS/WAXS measurements are performed using a SAXSLAB Ganesha 300XL.The wavelength of the incident X-rays is 1.54 Å using a micro-focussealed CuKα source. The X-rays are focused using a Silicon crystalmonochromator and beam size defined by a series of vertical andhorizontal slits. This slit configuration defines a beam size ofapproximately 0.3 mm on the sample. The scattered X-rays are collectedon a vacuum compatible Dectris Pilatus 300K 2D area detector. A pindiode measured the intensity after the sample and automatic correctionsfor sample transmission and beam intensity are done. The detector ismoved inside the vacuum tube to positions of 0.091 m, 0.441 m and 1.041m for WAXS, MAXS and SAXS respectively. This gives a q range of 0.07 to0.25 Å⁻¹, corresponding to real-space dimensions of 2.2 to 897 Å. Theestimated beam flux on the sample is 55×10⁶, 31×10⁶, and 4.5×10⁶photons/second for WAXS, MAXS, and SAXS configurations. The resulting 2Dpatterns are collected and collapsed into a 1D I(q) vs. q profile.

In embodiments, two, three, four, or more different layered silicatesupports may be present in the support. Likewise, two, three, four, ormore different layered silicate supports may be present in the polymerproduced herein.

In a preferred embodiment, the process described herein producespropylene homopolymers or propylene copolymers, such aspropylene-ethylene and/or propylene-α-olefin (preferably C₂, and/or C₄to C₂₀) copolymers (such as propylene-hexene copolymers,propylene-octene copolymers, or propylene-ethylene-hexene terpolymers)having a Mw/Mn of greater than 1 to 40 (preferably greater than 1 to 5).Preferably, copolymers of propylene have from 0 wt % to 25 wt %(alternately from 0.5 wt % to 20 wt %, alternately from 1 wt % to 15 wt%, preferably from 3 wt % to 10 wt %, preferably less than 1 wt %,preferably 0 wt %) of one or more of C₂ or C₄ to C₄₀ olefin comonomer(preferably ethylene or C₄ to C₂₀ or C₄ to C₁₂ alpha olefin comonomer,preferably ethylene, butene, hexene, octene, decene, dodecene,preferably ethylene, butene, hexene, or octene).

In another preferred embodiment, the process described herein producesethylene homopolymers or copolymers, such as ethylene-propylene and/orethylene-α-olefin (preferably C₃ and/or C₄ to C₂₀) copolymers (such asethylene-hexene copolymers, ethylene-octene copolymers, orethylene-propylene-hexene terpolymers) having a Mw/Mn of greater than 1to 40 (preferably greater than 1 to 5). Preferably, copolymers ofethylene have from 0 wt % to 25 wt % (alternately from 0.5 wt % to 20 wt%, alternately from 1 wt % to 15 wt %, preferably from 3 wt % to 10 wt%, preferably less than 1 wt %, preferably 0 wt %) of one or more of C₃to C₄₀ olefin comonomer (preferably propylene or C₃ to C₂₀ or C₄ to C₁₂alpha olefin comonomer, preferably propylene, butene, hexene, octene,decene, dodecene, preferably ethylene, butene, hexene, and octene).

In a preferred embodiment, the monomer is ethylene and the comonomer ishexene, preferably from 1 to 15 mol % hexene, alternately 1 to 10 mol %.

Typically, the polymers produced herein have an Mw of 1,000,000 to5,000,000 g/mol (preferably 1,500,000 to 4,000,000 g/mol) as measured byGPC.

Typically, the polymers produced herein have an Mw/Mn (“MWD” or “PDI”)of greater than 1 to 40 (alternately 1.2 to 20, alternately 2 to 10,alternately 2 to 5, alternately 2.5 to 4).

In a preferred embodiment, the polymer produced herein has a unimodal ormultimodal molecular weight distribution as determined by Gel PermeationChromotography (GPC). By “unimodal” is meant that the GPC trace has onepeak or inflection point. By “multimodal” is meant that the GPC tracehas at least two peaks or inflection points. An inflection point is thatpoint where the second derivative of the curve changes in sign (e.g.,from negative to positive or vice versa).

Unless otherwise indicated, GPC is performed as follows: A HighTemperature Gel Permeation Chromatography (Agilent PL-220), equippedwith three in-line detectors, a differential refractive index detector(DRI), a light scattering (LS) detector, and a viscometer is used.Experimental details, including detector calibration, are described in:T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules,Vol. 34, No. 19, pp. 6812-6820, (2001), and references therein. ThreeAgilent PLgel 10 μm Mixed-B LS columns are used. The nominal flow rateis 0.5 mL/min, and the nominal injection volume is 300 μL. The varioustransfer lines, columns, viscometer and differential refractometer (theDRI detector) are contained in an oven maintained at 145° C. Solvent forthe experiment is prepared by dissolving 6 grams of butylatedhydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a0.1 μm Teflon filter. The TCB is then degassed with an online degasserbefore entering the GPC-3D. Polymer solutions are prepared by placingdry polymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous shaking for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.284 g/ml at 145° C. The injectionconcentration is from 0.5 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector and the viscometer are purged. Flow rate in theapparatus is then increased to 0.5 ml/minute, and the DRI is allowed tostabilize for 8 hours before injecting the first sample. The LS laser isturned on at least 1 to 1.5 hours before running the samples. Theconcentration, c, at each point in the chromatogram is calculated fromthe baseline-subtracted DRI signal, I_(DRI), using the followingequation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and λ=690 nm. Units on parametersthroughout this description of the GPC-3D method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature DAWN HELEOS. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient. P(θ) is the formfactor for a monodisperse random coil, and K_(o) is the optical constantfor the system:

$K_{0} = \frac{4\pi^{2}{n^{2}\left( \frac{d\; n}{d\; c} \right)}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system, which take the same value as the one obtainedfrom DRI method. The refractive index, n=1.500 for TCB at 145° C. andλ=657 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(S), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram, iscalculated from the following equation:η_(S) =c[η]+0.3(c[η])²where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theGPC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

M_(V) is the viscosity-average molecular weight based on molecularweights determined by LS analysis. Z average branching index (g′z_(ave))is calculated using Ci=polymer concentration in the slice i in thepolymer peak times the mass of the slice squared, Mi².

In a preferred embodiment, the polymer produced herein has a compositiondistribution breadth index (CDBI) of 50% or more, preferably 60% ormore, preferably 70% or more, preferably 80% or more. CDBI is a measureof the composition distribution of monomer within the polymer chains andis measured by the procedure described in PCT publication WO 93/03093,published Feb. 18, 1993, specifically columns 7 and 8, as well as inWild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) andU.S. Pat. No. 5,008,204, including that fractions having a weightaverage molecular weight (Mw) below 15,000 are ignored when determiningCDBI.

In another embodiment, the polymer produced herein has two peaks in theTREF measurement. Two peaks in the TREF measurement as used in thisspecification and the appended claims means the presence of two distinctnormalized ELS (evaporation mass light scattering) response peaks in agraph of normalized ELS response (vertical or y axis) versus elutiontemperature (horizontal or x axis with temperature increasing from leftto right) using the TREF method below. A “peak” in this context meanswhere the general slope of the graph changes from positive to negativewith increasing temperature. Between the two peaks is a local minimum inwhich the general slope of the graph changes from negative to positivewith increasing temperature. “General trend” of the graph is intended toexclude the multiple local minimums and maximums that can occur inintervals of 2° C. or less. Preferably, the two distinct peaks are atleast 3° C. apart, more preferably at least 4° C. apart, even morepreferably at least 5° C. apart. Additionally, both of the distinctpeaks occur at a temperature on the graph above 20° C. and below 120° C.where the elution temperature is run to 0° C. or lower. This limitationavoids confusion with the apparent peak on the graph at low temperaturecaused by material that remains soluble at the lowest elutiontemperature. Two peaks on such a graph indicates a bi-modal compositiondistribution (CD). Bimodal CD may also be determined by other methodsknown to those skilled in the art. One such alternate method for TREFmeasurement that can be used, if the above method does not show twopeaks, is disclosed in B. Monrabal, “Crystallization AnalysisFractionation: A New Technique for the Analysis of BranchingDistribution in Polyolefins,” Journal of Applied Polymer Science, Vol.52, pp. 491-499, (1994).

TREF Method

Temperature Rising Elution Fractionation (TREF) analysis is done using aCRYSTAF-TREF 200+ instrument from Polymer Char, S.A., Valencia, Spain.The principles of TREF analysis and a general description of theparticular apparatus to be used are given in the article Monrabal, B.;del Hierro, P. Anal. Bioanal. Chem. 2011, 399, 1557. FIG. 3 of thearticle is an appropriate schematic of the particular apparatus used;however, the connections to the 6-port valve shown in FIG. 3 differ fromthe apparatus to be used in that the tubing connected to the 11-o'clockport is connected to the 9-o'clock port and the tubing connected to the9-o'clock port is connected to the 11-o'clock port. Pertinent details ofthe analysis method and features of the apparatus to be used are asfollows.

1,2-Dichlorobenzene (ODCB) solvent stabilized with approximately 380 ppmof 2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxytoluene)is used for preparing the sample solution and for elution. The sample tobe analyzed (approximately 25 mg, but as low as approximately 10 mg) isdissolved in ODCB (25 ml metered at ambient temperature) by stirring at150° C. for 60 min. A small volume (0.5 ml) of the solution isintroduced into a column (15-cm long by ⅜″ o.d.) packed with an inertsupport (of stainless stell balls) at 150° C., and the columntemperature is stabilized at 140° C. for 45 min. The sample volume isthen allowed to crystallize in the column by reducing the temperature to30° C. at a cooling rate of 1° C./min. The column is kept at 30° C. for15 min before injecting the ODCB flow (1 ml/min) into the column for 10min to elute and measure the polymer that did not crystallize (solublefraction). The infrared detector used (Polymer Char IR4) generates anabsorbance signal that is proportional to the concentration of polymerin the eluting flow. A complete TREF curve is then generated byincreasing the temperature of the column from 30 to 140° C. at a rate of2° C./min while maintaining the ODCB flow at 1 ml/min to elute andmeasure the dissolving polymer.

In a preferred embodiment of the invention, the polymer produced hereinhas a branching index (g'vis) of 0.95 or more, preferably 0.97 or more,preferably 0.98 or more.

In a preferred embodiment of the invention, the polymer produced hereinhas a bimodal composition distribution and a branching index (g'vis) of0.95 or more, preferably 0.97 or more, preferably 0.98 or more.

In a preferred embodiment of the invention, the polymer produced hereinhas a bulk density of 0.25 g/cc or more, preferably 0.30 to 0.80 g/cc,preferably greater than 0.32 g/cc. Bulk density is measured by quicklytransferring (in 10 seconds) the sample powder into a graduated cylinderwhich overflows when exactly 100 cc is reached. No further powder isadded at this point. The rate of powder addition prevents settlingwithin the cylinder. The weight of the powder is divided by 100 cc togive the density.

In embodiments, the polymers produced herein comprise at least 0.1 wt %layered silicate where the layered silicate has an average aspect ratio(L/W) of 1.5 or more, preferably from 1.5 to 10, preferably from 2 to 5,preferably from 2 to 4, as determined by Transmission ElectronMicroscopy.

In embodiments, the polymers produced herein comprise at least 0.1 wt %layered silicate where the layered silicate has an average aspect ratio(L/W) of 1.5 or more, preferably from 1.5 to 10, preferably from 2 to 5,preferably from 2 to 4, as determined by Transmission ElectronMicroscopy and have an Mw of 1,000,000 to 5,000,000 g/mol (preferably1,500,000 to 4,000,000 g/mol) as measured by GPC.

Average aspect ratio is determined by averaging the aspect ratio (lengthversus width) of multiple particles as shown in Transmission ElectronMicrographs. Several TEM photographs of the sample are taken and 60particles of layered silicate are identified and measured. For each ofthe 60 particles, the longest dimension is identified by drawing a linebetween the two points at the edge of the particle which are thefurthest apart (“length”). Then the shortest dimension is identified bydrawing a line between the two points at the edge of the particle whichare the least distance apart (“width”). Length is then divided by widthto obtain aspect ratio. The average aspect ratio is calculated as thearithmetical mean based on the aspect ratio of the 60 particles.Image-Pro Plus™ v 7.0.0 is used for image analysis.

When selecting the 60 particles for analysis: 1) only particles whichare entirely in the field of view are chosen for analysis; and 2)particles which exhibit signs of damage, such as rough fracture surfacesdue to handling, are not included in the analysis.

Uses of Polyolefins

Polyolefins prepared using the processes described herein find uses inall applications including fibers, injection molded parts, films, pipes,and wire and cable applications. Examples include carpet fibers andprimary and secondary carpet backing; slit tape applications, such astarpaulins, erosion abatement screens, sand bags, fertilizer and feedbags, swimming pool covers, intermediate bulk container (IBC) bags;non-woven applications for spun-bonded, melt blown and thermobondedfibers; carded web applications, such as disposable diaper liners,feminine hygiene products, tarpaulins and tent fabrics, and hospitalgarments; apparel applications, such as socks, T-shirts, undergarments,bicycle shorts, sweat bands, football undershirts, hiking socks, andother outdoor sporting apparel; cordage applications, such as mooringand towing lines and rope; netting applications, such as safety fencesand geogrids for soil stabilization; injection molded applications suchas appliance parts in automatic dishwashers and clothes washers, handtools, and kitchen appliances; consumer product applications, such asoutdoor furniture, luggage, infant car seats, ice coolers, yardequipment; medical applications, such as disposable syringes and otherhospital and laboratory devices; rigid packaging made by injectionmolding, blow molding, or thermoforming such as margarine tubs, yogurtcontainers and closures, commercial bottles, and ready-to-eat foodcontainers; transportation applications, such as automotive interiortrim, instrument panels, bumper fascia, grills and external trim parts,battery cases; film applications, such as snack packages and other foodpackaging and film labels, packing tapes and pressure sensitive labels;wire and cable applications, such as wire insulation.

The polyolefins described herein may be used by themselves or blendedwith one or more additional polymers. In another embodiment, thepolyolefin (preferably propylene or ethylene homopolymer or copolymer)produced herein is combined with one or more additional polymers priorto being formed into a film, molded part, or other article. Usefuladditional polymers include polyethylene, isotactic polypropylene,highly isotactic polypropylene, syndiotactic polypropylene, randomcopolymer of propylene and ethylene, and/or butene, and/or hexene,polybutene, ethylene vinyl acetate, LDPE (low density polyethylene),LLDPE (linear low density polyethylene), HDPE (high densitypolyethylene), ethylene vinyl acetate, ethylene methyl acrylate,copolymers of acrylic acid, polymethylmethacrylate or any other polymerspolymerizable by a high-pressure free radical process,polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins,ethylene-propylene rubber (EPR), vulcanized EPR, EPDM(ethylene-propylene-diene monomer rubber), block copolymer, styrenicblock copolymers, polyamides, polycarbonates, PET (polyethyleneterephthalate) resins, cross linked polyethylene, copolymers of ethyleneand vinyl alcohol (EVOH), polymers of aromatic monomers such aspolystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride,polyethylene glycols, and/or polyisobutylene.

This invention further relates to:

1. A process to polymerize olefins comprising:

i) contacting olefins with a catalyst system comprising: 1) supportcomprising an organoaluminum treated layered silicate and inorganicoxide and 2) pyridyldiamido compound represented by the Formula (A):

wherein:M* is a Group 4 metal;

each E′ group is independently selected from carbon, silicon, orgermanium;

each X′ is an anionic leaving group;

L* is a neutral Lewis base;

R′¹ and R′¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;

R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, and R′¹² areindependently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphino;

n′ is 1 or 2;

m′ is 0, 1, or 2; and

two X′ groups may be joined together to form a dianionic group;

two L* groups may be joined together to form a bidentate Lewis base;

an X′ group may be joined to an L* group to form a monoanionic bidentategroup;

R′⁷ and R′⁸ may be joined to form a ring; and

R′¹⁰ and R′¹¹ may be joined to form a ring; and

ii) preferably, obtaining a polyolefin composition, A, having an Mw of1,000,000 g/mol or more and comprising 5 wt % or less of the layeredsilicate, where polyolefin composition A has: 1) no diffraction peakresulting from interlamellar spacing of the organoaluminum treatedlayered silicate, and/or 2) a diffraction peak resulting frominterlamellar spacing of the organoaluminum treated layered silicate ofZ Angstroms or more, where Z=5X, where X is the diffraction peakresulting from interlamellar spacing of the support before combinationwith the catalyst compound, as measured by wide angle x-ray scattering.2. The process of paragraph 1, wherein the pyridyldiamido compound isrepresented by the Formula (I):

wherein:M is a Group 4 metal;Z is —(R¹⁴)_(p)C—C(R¹⁵)_(q)—,where R¹⁴ and R¹⁵ are independently selected from the group consistingof hydrogen, hydrocarbyls, and substituted hydrocarbyls, and whereinadjacent R¹⁴ and R¹⁵ groups may be joined to form an aromatic orsaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ringcan join to form additional rings,p is 0, 1, or 2, andq is 0, 1, or 2;R¹ and R¹¹ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R² and R¹⁰ are each, independently, -E(R¹²)(R¹³)— with E being carbon,silicon, or germanium, and each R¹² and R¹³ being independently selectedfrom the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl,amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino, R¹²and R¹³ may be joined to each other or to R¹⁴ or R¹⁵ to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R¹² and R¹³ may be joined to forma saturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings;R³, R⁴, and R⁵ are independently selected from the group consisting ofhydrogen, hydrocarbyls (such as alkyls and aryls), substitutedhydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and whereinadjacent R groups (R³ & R⁴ and/or R⁴ & R⁵) may be joined to form asubstituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring atoms and where substitutions on the ringcan join to form additional rings;L is an anionic leaving group, where the L groups may be the same ordifferent and any two L groups may be linked to form a dianionic leavinggroup;n is 0, 1, 2, or 3;L′ is a neutral Lewis base; andw is 0, 1, 2, or 33. The process of paragraph 2, wherein the pyridylamido compound isrepresented by the Formula II:

wherein:R⁶, R⁷, R⁸, and R⁹ are independently selected from the group consistingof hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen,amino, and silyl, and wherein adjacent R groups (R⁶& R⁷ and/or R⁷& R⁸and/or R⁸& R⁹, and/or R⁹& R¹⁰) may be joined to form a saturated,substituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring carbon atoms and where substitutions on thering can join to form additional rings; andM, L, L′, w, n, R¹, R², R³, R⁴, R⁵, R¹⁰, and R¹¹ are as defined in claim2.4. The process of paragraph 2, wherein the pyridylamido compound isrepresented by the Formula III:

wherein:R⁶, R⁷, R⁸, R⁹, R¹⁶, and R¹⁷ are independently selected from the groupconsisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy,halogen, amino, and silyl, wherein adjacent R groups (R⁶ & R⁷ and/or R⁷& R¹⁶ and/or R¹⁶ & R¹⁷, and/or R⁸ & R⁹) may be joined to form asaturated, substituted or unsubstituted hydrocarbyl or heterocyclicring, where the ring has 5, 6, 7, or 8 ring carbon atoms and wheresubstitutions on the ring can join to form additional rings; andM, L, L′, w, n, R¹, R², R³, R⁴, R⁵, R¹⁰, and R¹¹ are as defined inparagraph 2.5. The process of paragraph 2 or 3, wherein M is zirconium or hafnium.6. The process of paragraph 1, wherein M* is hafnium.7. The process of any of paragraphs 2 to 5, wherein each of R¹, R², R³,R⁴, R⁵, R¹⁰, and R¹¹ is, independently, hydrogen or a hydrocrbyl.8. The process of any of paragraphs 1 to 7, wherein the combination oflayered silicate and inorganic oxide is spray dried prior to contactwith the organoaluminum.9. The process of paragraph 8, wherein the support is obtained by spraydrying an aqueous slurry of alkylaluminum treated layered silicate and aGroup 1 or 2 silicate.10. The process of paragraph 8, wherein the support is obtained by spraydrying an aqueous slurry of trialkyl aluminum treated montmorillonite,where the alkyl is a C1 to C12 alkyl group, and a sodium, potassium,lithium, or magnesium silicate, or a mixture thereof.11. The process of any of paragraphs 1 to 10, wherein the supportcomprises spheroidal particles of the combination of the organoaluminumtreated layered silicate and the inorganic oxide.12. The process of any of paragraphs 1 to 11, wherein the supportcomprises particles having an average diameter of 20 to 100 microns.13. The process of any of paragraphs 1 to 12, wherein the supportcomprises particles having a pore volume of between 0.1 and 0.4 cc/g.14. The process of any of paragraphs 1 to 13, wherein the supportcomprises particles having a surface area of between 100 and 200 m²/g.15. The process of any of paragraphs 1 to 14, wherein the supportcomprises at least 10 wt % montmorillonite, based upon the weight of theorganoaluminum treated layered silicate and the inorganic oxide.16. The process of any of paragraphs 1 to 15, wherein the supportcomprises 50 to 90 wt % montmorillonite, based upon the weight of theorganoaluminum treated layered silicate and the inorganic oxide.17. The process of any of paragraphs 1 to 16, wherein the organoaluminumcomprises trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, tri-iso-octylaluminum,triphenylaluminum, or a combination thereof.18. The process of any of paragraphs 1 to 17, wherein the polyolefin hasa bulk density of 0.25 g/ml.19. The process of any of paragraphs 1 to 18, wherein the polyolefin hasno diffraction peak resulting from interlamellar spacing of theorganoaluminum treated layered silicate.20. The process of any of paragraphs 1 to 19, wherein the polyolefin isan ethylene polymer.21. The process of any of paragraphs 1 to 19, wherein the polyolefin isan ethylene homopolymer.22. The process of any of paragraphs 1 to 21, wherein the polyolefin isan ethylene copolymer.23. The process of any of paragraphs 1 to 22, wherein the polyolefin hasan Mw from 1,000,000 to 3,000,000 g/mol.24. The process of any of paragraphs 1 to 23, wherein the polymerizationis conducted in the gas phase.25. The process of any of paragraphs 1 to 23, wherein the polymerizationis conducted in the slurry phase.26. The process of any of paragraphs 1 to 25, wherein alumoxane isabsent.27. The process of any of paragraphs 1 to 26, wherein non-coordinatinganion is absent.28. The process of any of paragraphs 1 to 26, wherein the supportcomprising an organoaluminum treated layered silicate support andinorganic oxide has an aspect ratio of 1 to 1.7.29. The process of any of paragraphs 1 to 26, wherein the catalystsystem has an average aspect ratio of 1 to 1.7.30. An ethylene polymer having an Mw of 1,000,000 g/mol or more andcomprising 0.1 to 5 wt % of a layered silicate, where the ethylenepolymer has no diffraction peak resulting from interlamellar spacing ofthe layered silicate, as measured by wide angle x-ray scattering.31. An ethylene polymer having an Mw of 1,000,000 g/mol or more andcomprising 0.1 to 5 wt % of a layered silicate derived from a supportedcatalyst used to produce the ethylene polymer, where the ethylenepolymer has 1) no diffraction peak resulting from interlamellar spacingof the layered silicate present in the supported catalyst, and 2) adiffraction peak resulting from interlamellar spacing of the layeredsilicate of Z Angstroms or more, where Z=5X, where X is the diffractionpeak resulting from interlamellar spacing of the layered silicatepresent in the supported catalyst, as measured by wide angle x-rayscattering.

EXAMPLES

The following abbreviations may be used below: eq. means equivalents.

All reagents were obtained from Sigma Aldrich (St. Louis, Mo.) and usedas obtained, unless stated otherwise. All solvents were anhydrous. Allreactions were performed under an inert nitrogen atmosphere, unlessotherwise stated. All deuterated solvents were obtained from CambridgeIsotopes (Cambridge, Mass.) and dried over 3 Angstrom molecular sievesbefore use.

Products were Characterized as Follows:

¹H NMR

Unless otherwise indicated, ¹H NMR data of non-polymeric compounds wascollected at room temperature in a 5 mm probe using either a Bruker orVarian NMR spectrometer operating with a ¹H frequency of 400 or 500 MHz.Data was recorded using a 30° flip angle RF pulse, 8 scans, with a delayof 5 seconds between pulses. Samples were prepared using approximately5-10 mg of compound dissolved in approximately 1 mL of an appropriatedeuterated solvent, as listed in the experimental examples. Samples arereferenced to residual protium of the solvents at 7.15, 7.24, 5.32,5.98, and 2.10 for D5-benzene, chloroform, D-dichloromethane,D-1,1,2,2-tetrachloroethane, and C₆D₅CD₂H, respectively. Unless statedotherwise, NMR spectroscopic data of polymers was recorded in a 5 mmprobe on a Varian NMR spectrometer at 120° C. using ad₂-1,1,2,2-tetrachloroethane solution prepared from approximately 20 mgof polymer and 1 mL of solvent. Unless stated otherwise, data wasrecorded using a 30° flip angle RF pulse, 120 scans, with a delay of 5seconds between pulses.

All molecular weights are weight average unless otherwise noted. Allmolecular weights are reported in g/mol unless otherwise noted.

Experimental

Catalysts A, B, C, and D (also referred to as Complexes A, B, C, and D)are depicted in FIG. 1.

Synthesis of Pyridyldiamide Complexes.

Complex A was prepared as described in US 2014/0221587. Complex C wasprepared as described in US 2015/0141601A1. Complex D was prepared usinga procedure analogous to that used for complex A. The only significantdifference was that a different aniline was used during the synthesis ofthe pyridyldiamine ligand. Complex B was prepared using the series ofreactions described below.

4,4,5,5-Tetramethyl-2-(2-methyl-1-naphthyl)-1,3,2-dioxaborolane (1)

1,2-Dibromoethane (˜0.3 ml) was added to 6.10 g (0.25 mol) of magnesiumturnings in 1000 cm³ of THF. This mixture was stirred for 10 min, andthen 55.3 g (0.25 mol) of 1-bromo-2-methylnaphtalene was added byvigorous stirring for 3.5 h at room temperature. Further on, 46.5 g (250mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was addedin one portion. The resulting mixture was stirred for 15 min and thenpoured into 1000 cm³ of cold water. The product was extracted with 3×300ml of ethyl acetate. The organic layer was separated, washed by water,brine, dried over MgSO₄, and, finally, evaporated to dryness. The formedwhite solid was washed by 2×75 ml of pentane and then dried in vacuum.Yield 47.3 g (70%). Anal. calc. for C₁₇H₂₁BO₂: C, 76.14; H, 7.89. Found:C, 76.21; H, 7.96. ¹H NMR (CDCl₃): δ 8.12 (m, 1H, 8-H), 7.77 (m, 1H,5-H), 7.75 (d, J=8.4 Hz, 1H, 4-H), 7.44 (m, 1H, 7-H), 7.38 (m, 1H, 6-H),7.28 (d, J=8.4 Hz, 1H, 3-H), 2.63 (s, 3H, 2-Me), 1.48 (s, 12H,CMe₂CMe₂).

2-[2-(Bromomethyl)-1-naphthyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2)

A mixture of 47.3 g (176 mmol) of4,4,5,5-tetramethyl-2-(2-methyl-1-naphthyl)-1,3,2-dioxaborolane, 33.0 g(185 mmol) of NBS, and 0.17 g (0.70 mmol) of benzoyl peroxide in 340 mlof CCl₄ was stirred in argon atmosphere for 14 h at 75° C. The resultingmixture was cooled to room temperature, filtered through a glass frit(G3), and the filtrate was evaporated to dryness. This procedure gave62.2 g (99%) of a beige solid. Anal. calc. for C₁₇H₂₀BBrO₂: C, 58.83; H,5.81. Found: C, 58.75; H, 5.90. ¹H NMR (CDCl₃): δ 8.30 (m, 1H, 8-H),7.84 (d, J=8.3 Hz, 1H, 4-H), 7.79 (m, 1H, 5-H), 7.43-7.52 (m, 3H,3,6,7-H), 4.96 (s, 2H, CH₂Br), 1.51 (s, 12H, CMe₂CMe₂).

Cyclohexyl{[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}amine(3)

A mixture of 18.0 g (181 mmol) of cyclohexylamine, 42.1 (129 mmol) g of2-[2-(bromomethyl)-1-naphthyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,18.4 g (133 mmol) of K₂CO₃, and 500 ml of DMF was stirred for 12 h at80° C. in argon atmosphere. The resulting mixture was poured into 1200ml of water. The product was extracted with 3×200 ml of ethyl acetate.The combined extract was dried over Na₂SO₄ and then evaporated todryness. An excess of cyclohexylamine was distilled off using theKugelrohr apparatus. Yield 29.9 g (67%) of a dark red glassy solid.Anal. Calc for C₂₃H₃₂BNO₂: C, 75.62; H, 8.83; N, 3.83. Found: C, 75.69;H, 8.79; N, 3.87. ¹H NMR (CDCl₃): δ 8.51 (m, 1H, 8-H in naphtyl), 7.76(m 1H, 4-H in naphtyl), 7.69 (m, 1H, 5-H in naphtyl), 7.41-7.46 (m, 1H,7-H in naphtyl), 7.35-7.39 (m, 1H, 6-H in naphtyl), 7.18 (m, 1H, 3-H innaphtyl), 4.16 (s, 2H, CH₂), 3.32 (m, 1H, NH), 1.56-1.67 (m, 5H, Cy),1.37 (s, 12H, BPin), 1.15-1.25 (m, 5H, Cy), 0.94-1.06 (m, 1H, Cy).

6-{2-[(Cyclohexylamino)methyl]-1-naphthyl}pyridine-2-carbaldehyde (4)

A solution of 21.2 g (74.1 mmol) of Na₂CO₃×10H₂O in 660 ml of water and190 ml of methanol was purged with argon for 30 min. The obtainedsolution was added to a mixture of 29.9 g (80.0 mmol) of cyclohexyl{[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}amine,14.0 g (80.0 mmol) of 6-bromopyridine-2-carbaldehyde, 4.62 g (4.00 mmol)of Pd(PPh₃)₄, and 780 ml of toluene in argon atmosphere. This mixturewas refluxed for 10 h using a mechanical stirrer, then cooled to roomtemperature. The organic layer was separated, dried over Na₂SO₄,evaporated to 300 ml in volume, and then extracted with 3×300 ml of 2MHCl. The combined aqueous layer was alkalified to pH 10 by the saturatedaqueous K₂CO₃, and then extracted with 3×200 ml of dichloromethane. Thecombined organic extract was dried over Na₂SO₄ and evaporated todryness. Yield 23.1 g (84%) of a brown oil. Anal. Calc for C₂₃H₂₄N₂O: C,80.20; H, 7.02; N, 8.13. Found: C, 80.78; H, 7.11; N, 8.01. ¹H NMR(CDCl₃): δ 10.08 (s, 1H, CHO), 7.96-8.03 (m, 2H, 3-H, 4-H in Py),7.83-7.89 (m, 2H, 8.5-H in Py), 7.59-7.64 (m, 2H, 5-H in Py and 4-H innaphtyl), 7.39-7.43 (m, 1H, 6-H in naphtyl), 7.30-7.34 (m, 1H, 7-H innaphtyl), 7.20-7.23 (m, 1H, 3-H in naphtyl), 3.56 (m, 2H, CH₂), 2.21 (m,1H, 1-H in Cy), 1.57-1.66 (m, 4H, Cy), 1.02-1.11 (m, 4H, Cy), 0.88-0.96(m, 2H, Cy).

N-[(1E)-(6-{2-[(Cyclohexylamino)methyl]-1-naphthyl}pyridin-2-yl)methylene]-2,6-diisopropylaniline(5)

A solution of 9.80 g (28.0 mmol) of6-{2-[(cyclohexylamino)methyl]-1-naphthyl}pyridine-2-carbaldehyde, 5.55g (31.0 mmol) of 2,6-diisopropylaniline, 0.1 g of TsOH in 100 ml of dryethanol was refluxed for 10 h in argon atmosphere. The resulting mixturewas cooled to room temperature and then evaporated to dryness. Theresidue was purified by flash chromatography on silica gel 60 (40-63 um,eluent: hexane-ethyl acetate-triethylamine=10:1:1, vol.). Yield 10.8 g(77%) of yellow powder. Anal. Calc for C₃₅H₄₁N₃: C, 83.45; H, 8.20; N,8.34. Found: C, 83.59; H, 8.06; N, 8.41. ¹H NMR (CDCl₃): δ 8.39 (m, 1H,3-H in Py), 8.35 (s, 1H, CHN), 8.00 (m, 1H, 4-H in Py), 7.87-7.92 (m,2H, 4.8-H in naphtyl), 7.63 (m, 1H, 3-H in naphtyl), 7.54 (m, 1H, 3-H inPy), 7.37-7.47 (m, 3H, 5-H in Py and 6.7-H in naphtyl), 7.09-7.17 (m,3H, 3,4,5-H in naphtyl), 3.69 (m, 2H, CH₂N), 3.01 (sept, J=6.8 Hz, 2H,CH in 2,6-diisopropylphenyl), 2.29 (m, 1H, CH in Cy), 1.61-1.72 (m, 4H,Cy), 1.52-1.54 (m, 2H, Cy), 1.19 (d, J=6.8 Hz, 12H, CH₃ in2,6-diisopropylphenyl), 1.09-1.11 (m, 2H, Cy), 0.94-0.99 (m, 2H, Cy).

N-[(6-{2-[(Cyclohexylamino)methyl]-1-naphthyl}pyridin-2-yl)(2-isopropylphenyl)methyl]-2,6-diisopropylaniline

To a solution of 3.56 g (18.0 mmol) of 2-isopropylbromobenzene in 80 mlof THF 21.0 ml (35.7 mmol) of 1.7M ^(t)BuLi in pentane was added at −80°C. in argon atmosphere. The resulting solution was stirred for 1 h atthis temperature. Then, a solution of 3.00 g (6.00 mmol) ofN-[(1E)-(6-{2-[(cyclohexylamino)methyl]-1-naphthyl}pyridin-2-yl)methylene]-2,6-diisopropylanilinein 20 ml of THF was added. The obtained mixture was stirred for 30 minat −80° C. Further on, 10 ml of water was added, and this mixture waswarmed to room temperature. The resulting mixture was diluted with 100ml of water, and crude product was extracted with 50 ml of ethylacetate. The organic layer was separated, dried over Na₂SO₄, andevaporated to dryness. The residue was purified by flash chromatographyon silica gel 60 (40-63 um, eluent: hexane-ethylacetate-triethylamine=10:1:1, vol.). Yield 1.15 g (31%) of a yellowglassy solid. Anal. Calc for C₄₄H₅₃N₃: C, 84.70; H, 8.56; N, 6.73.Found: C, 84.86; H, 8.69; N, 6.55. ¹H NMR (CDCl₃): δ 7.87 (m); 7.59-7.74(m); 7.42-7.46 (m); 7.14-7.34 (m); 6.99 (m); 5.52 (d); 5.39 (d); 4.80(m); 4.50 (m); 3.67 (m); 3.48-3.58 (m); 3.18 (m); 2.98 (m); 2.50-2.55(m); 2.15 (m); 2.25 (m); 1.48-1.72 (m); 1.03-1.15 (m); 0.98-1.01 (m);0.91-0.93 (m); 0.79-0.86 (m).

Complex B.

While shielded from direct light,N-[(6-{2-[(Cyclohexylamino)methyl]-1-naphthyl}pyridin-2-yl)(2-isopropylphenyl)methyl]-2,6-diisopropylaniline(0.898 g, 1.44 mmol), Hf(NMe₂)₂Cl₂(dme) (0.616 g, 1.44 mmol), andtoluene (20 mL) were combined and heated to 95° C. in a round bottomedflask that was uncapped to allow for the release of dimethylamine. After3 h, the volatiles were evaporated under a stream of nitrogen to afforda yellow solid that was washed thoroughly with Et₂O to afford 1.11 g(1.27 mmol) of the dichloride complex. This dichloride intermediate wasdissolved in CH₂Cl₂ (20 mL) and Me₂Mg in Et₂O (4.43 mL, 1.4 mmol) wasadded dropwise. After 30 minutes, the volatiles were evaporated under astream of nitrogen and the residue was dried thoroughly under reducedpressure. The residue was extracted with CH₂Cl₂ (10 mL) and filtered.Concentration of this solution to 1 mL followed by the addition ofpentane (3 mL) caused the product to precipitate as a yellowmicrocrystalline solid. Yield 0.99 g, 83%. Room temperature H-NMRspectroscopic analysis indicates that the product is an 85:15 mixture ofrotational diastereomers.

Supported Catalysts:

Supportation of Complex a on Spray Dried Montmorrillonite.

K10 montmorillonite was purchased from Sigma-Aldrich and used asreceived. Montmorillonite KSF was purchased from Sigma-Aldrich.Methylalumoxane 30 wt % in toluene was purchased from Albemarle and usedas received. Trimethyl aluminum, triethyl aluminum and tri-n-octylaluminum were purchased from Akzo Nobel and used as received.

Spray Dried Montmorillonite, Support 1

Support 1 was prepared by adding 2500 g of montmorillonite (K-10,Sigma-Aldrich) to 3.4 l of deionized water. A homogeneous slurry, withan agglomerate size d₅₀ typically in the range of 15 μm, was achieved bystirring with a high-shear mixer for 60 min. Then 27 g of sodiumsilicate (reagent grade, Aldrich) were added to the mixture andhomogenized for 5 min; achieving a final solids content of 30 wt %. Theobtained slurry was spray dried at a rate of 300 cc/min using a Bowenspray drier with an inlet temperature in the range of 716° F. and 1100°F. (380° C. and 593° C.), depending on feed flow, and a target outlettemperature of 320° F. (160° C.). The product was recovered as a dry,flowing powder with an agglomerate size d₅₀ between 90 and 150 μm, andmoisture content between 17 and 6 wt %, depending on spray gas pressure.Finally, the support was dried further at 121° F. (250° C.) for 16 h andoptionally calcined in air at 932° F. (500° C.) for 8 h.

Sulfuric Acid Treated Montmorillonite KSF, Support 2

Montmorillonite KSF was then treated according to the general procedureof Example 1 of U.S. Pat. No. 7,220,695, i.e., Montmorillonite KSF(198.766 g) was placed in a 2 L round bottom flask along with 1.40 L ofH₂O and 110 mL of concentrated sulfuric acid and stirred for 6 hr at 90°C. The mixture was then allowed to stir overnight at room temperature.The mixture was filtered and the solid was washed with 4×1 L of H₂O. ThepH of the filtrate was monitored; when the pH was approximately 3 thewashing was stopped and the solid was heated to 130° C. while open toair. The solid was then placed under vacuum at room temperature for afew hours and then heated to 150° C. under vacuum overnight. The claywas brought into a glovebox while maintaining a nitrogen atmosphere. A132 gram amount of tan solid was obtained as Support 2.

Tri-n-Octyl Aluminum Treated Montmorillonite KSF, Support 3

Support 2 (14.9 grams) was slurried in 100 mls of toluene. The slurrywas sonicated for 5 minutes. Tri-n-octylaluminum (10.25 grams, 27.9485mmol) was dissolved in 5 mLs of toluene and added to the slurry. Theslurry was sonicated for an hour at 60° C. ¹H NMR analysis of thesolvent indicated excess tri-n-octyl aluminum in solution. The solid wasfiltered and washed three times with 50 mLs of toluene and once withpentane. The solid was dried under vacuum, yielding 15.6 grams of tansolid as Support 3.

Complex A on Tri-n-Octyl Aluminum Treated Montmorillonite KSF, SupportedComplex A

Support 3 was slurried in 50 mL of toluene in a beaker and sonicated for5 minutes. Complex A was dissolved in 7 mL of toluene and added to theslurry, which was then sonicated for an additional 30 minutes. Theslurry was filtered, washed three times with 20 mL of toluene, and twotimes with pentane. The solid was dried under vacuum overnight to give0.953 grams of tan solid as Supported Complex A.

Example 1: Polymerization with Supported Complex A

Tri-n-octylaluminum (2 mL, 0.091M in hexane) was injected into a 2 literautoclave reactor that had been baked out for 1 hour. 500 milliliters ofisohexane was then added to the reactor. The stir rate was set to 500rpm and temperature set at 85° C. Supported Complex A (0.0531 g) wasinjected into the reactor with 200 mL of isohexane. The reactor waspressurized with 150 psi of ethylene. The reactor was stirred for 1 hourkeeping the reactor at a total psi of 330 psi. After 1 hour the reactorwas vented and cooled to room temperature. 170 milligrams ofpolyethylene resin was obtained.

Tri-Ethyl Aluminum Treated Montmorillonite K-10, Support 4

Support 1 (4.53 grams) was slurried in 40 milliters of toluene in aCelstir flask. Triethylaluminum (1.81 g, 15.9 mmol, 3.50 mmol/g) wasadded neat to the Celstir. The slurry stirred for 1 hour at 60° C. Thesolid was filtered, washed three times with 25 milliliters of tolueneand two times with pentane. The solid was dried under vacuum, giving4.58 grams of gray solid as Support 4.

Tri-Methyl Aluminum Treated Montmorillonite K-10, Support 5

Support 1 (4.2634 g) was slurried in 30 mL of toluene. Trimethylaluminum(0.2420 g, 3.357 mmol) was dissolved in 10 mL of toluene added slowly tothe slurry. The slurry was stirred at 60° C. for 1 hr. ¹H NMR analysisshowed an excess of trimethylaluminum. The slurry was then filtered,washed three times with 20 mL of toluene each and washed twice withpentane. The solid was dried under vacuum to give 4.28 g of tan materialas Support 5.

Tri-Isobutyl Aluminum Treated Montmorillonite K-10, Support 6

Support 1 (4.76 g) was slurried in 25 mL of toluene. Triisobutylaluminum(0.733 g, 3.70 mmol) was dissolved in 10 mL of toluene added slowly tothe slurry. The slurry was stirred at 60° C. for 1 hr. ¹H NMR analysisshowed an excess of triisobutylaluminum. The slurry was then filtered,washed three times with 20 mL of toluene each and washed twice withpentane. The solid was dried under vacuum to give 4.88 g of tan materialas Support 6.

Supportation of Complex A on Support 4

Support 4 was slurried in 15 mL of toluene at high speed. Complex A(29.0 mg, 0.0382 mmol, 0.0398 mmol/g) was dissolved in 5 mL of tolueneand added to the slurry. The slurry stirred for 1 hour before beingfiltered, washed three times with 20 mL portions of toluene and twicewith pentane. The solid was dried under vacuum, giving 0.938 grams oftan solid.

Surface area Pore Volume (BET method) (BJH Adsorption Support m²/gcumulative volume) cm³/g Montmorillonite MKSF 33.3 0.0257 Support 1 2040.257 Support 4 169 0.226 Support 6 166 0.227Supportation of Complex A on Support 5

Support 5 (0.5714 g) was slurried in 10 mL of toluene at high speed.Complex A (17.2 mg, 0.0227 mmol) was dissolved in 5 mL of toluene andadded to the slurry. The slurry was stirred for 1 hr, filtered, washedthree times with 15 mL of toluene each, and washed twice with pentane.The solid was dried under vacuum to give a tan solid.

Supportation of Complex B, on Support 4

Support 4 was slurried in 15 mL of toluene at high speed. Complex B(21.8 mg, 0.0263 mmol) was dissolved in 5 mL of toluene and added to theslurry. The slurry stirred for 1 hr before being filtered, washed threetimes with 20 mL of toluene and twice with pentane. The solid was driedunder vacuum, giving 0.6241 g of tan solid.

Supportation of Complex C, on Support 4

Support 4 (0.6510 g) was slurried in 15 mL of toluene at high speed.Complex C (17.7 mg, 0.0259 mmol) was dissolved in 5 mL of toluene andadded to the slurry. The slurry stirred for 1 h before being filtered,washed three times with 20 mL of toluene and twice with pentane. Thesolid is dried under vacuum, giving 0.6118 g of tan solid.

Supportation of Complex D, on Support 4

Support 4 (0.4087 g) was slurried in 15 mL of toluene at high speed.Complex D (12.1 mg, 0.0162 mmol) was dissolved in 5 mL of toluene andadded to the slurry. The slurry stirred for 1 h before being filtered,washed three times with 20 mL of toluene and twice with pentane. Thesolid was dried under vacuum, giving 0.3901 g of tan solid.

Supportation of Complex A on MAO Treated Silica

600° C. calcined Davison™948 silica (45.6903 g) was slurried in 250 mLof toluene and heated to 80° C. Methyl alumoxane MAO (79.25 g of a 30%wt solution in toluene) was added slowly to the slurry, producing somebubbling. The slurry was stirred for 1 hour. The slurry was filtered,washed twice with 25 mL of toluene and dried under vacuum for two days.A 68.11 gram amount of white solid was obtained. The white solid (0.7835g) was slurried in 20 mL of toluene. Complex A (23.7 mg, 0.0312 mmol)was dissolved in 5 mL of toluene. The catalyst was added to the slurryand stirred for 2 hr. The slurry was filtered, washed twice with 20 mLof toluene, washed once with pentane, and dried under vacuum overnight.Collected 0.7376 g of white solid.

Polymerization Example 2: Complex A on Spray DriedMontmorillonite-K10-TEAL

Tri-ethyl aluminum, (2 mL, 0.091M in hexane) was injected into a 2 literautoclave that had been baked out for 1 hour. 800 mL of isohexane wasthen added to the reactor. The stir rate was set to 500 rpm andtemperature set at 85° C. The reactor was pressurized with 60 psi ofethylene. Supported complex A (0.0907 g) was slurried with 2 mL ofpentane and injected with another 62 psi of ethylene. The reaction wasrun for 30 min. The catalyst tube was plugged during the injectionprocess. A 14.57 gram amount of white granules was obtained. Activity:321 g polymer/(g cat*hr).

Polymerization Example 3: Complex D on Spray DriedMontmorillonite-K10-TEAL

Tri-ethylaluminum (2 mL, 0.091M in hexane) was injected into a 2 Literautoclave reactor that had been baked out for 1 hour. A 300 mL amount ofisohexane was then added to the reactor. 5 milliliters of 1-hexene wasadded to the reactor followed by an additional 300 milliliters ofisohexane. The stir rate was set to 500 rpm and temperature set at 85°C. The reactor was pressurized with 20 psi of ethylene. Supportedcomplex D (0.0712 g) was injected along with 2 milliliters of pentaneand pushed in with 200 milliliters of isohexane. The reactor waspressurized to give a total ethylene pressure of 130 psi. Thepolymerization was run for 30 minutes. A 15.8 gram amount of whitegranules obtained. Activity: 444 g polymer/(g cat*hr).

Polymerization Example 4

Support 4 (0.571 grams) was weighed out in a vial. Toluene (14 mL) andtriisobutyl aluminum (0.569 g, 2.87 mmol) was then added to the vial.The vial was shaken for 5 min. Complex A (17.8 mg, 0.0235 mmol) was thenadded to the vial. The vial was placed on a shaker for 5 hrs. The slurrywas removed via syringe in about 2 mL quantities for use inpolymerization reactions.

Tri-ethylaluminum (2 mL, 0.091M in hexane) was injected into a 2 literautoclave reactor that had been baked out for 1 hour. A 300 mL amount ofisohexane was then added to the reactor. 10 or 0 milliliters of 1-hexenewas added to the reactor followed by an additional 300 milliliters ofisohexane. The stir rate was set to 500 rpm and temperature set at 85°C. The reactor was pressurized with 20 psi of ethylene. 2 mls of thecatalyst slurry was injected along with 2 mls of pentane and pushed inwith 200 mls of isohexane. The reactor was pressurized to give a totalethylene pressure of 130 psi.

Reaction with 10 mls of hexene yielded 29.9 grams of PE (731gPE/gsupcat.hr). Reaction with no hexene yielded 9.91 grams of PE.

Examples 4-15

The procedure of Example 3 was repeated with alternate supportedcatalyst complexes. The data are reported in Table 1.

TABLE 1 Catalyst Hexene Yield Bulk Mn Mw Example Precursor Support (mls)(grams) Activity** Density (g/mol)* (g/mol)* Mw/Mn 4 (1-Me,3- 4 0 14.62558.6 BuCp)₂ZrMe₂ 1 Complex A 3 0.170 5 Complex A 4 0 14.6 321 0.3038732,694 1,757,025 2.40 3 Complex A 4 5 15.8 444 0.2898 1,187,0902,643,660 2.23 6 Complex A 4 10 9.79 413.3 0.2848 967,202 2,212,854 2.297 Complex A 5 0 7.6 261.2 894,488 2,247,868 2.51 8 Complex A 5 10 10.3361.5 894,144 2,155,165 2.41 Complex A 6 0 11.6 413 0.3420 Complex A 610 21.1 767 0.2376 9 Complex A MAO 10 11.68 520,158 1,762,383 3.39treated Silica 10 Complex B 4 10 14.7 589 0.2490 11 Complex B 4 0 27.0859 0.2776 12 Complex C 4 10 16.1 510 0.1960 13 Complex C 4 0 15.0 4760.2022 14 Complex D 4 10 2.42 126 15 Complex D 4 0 3.0 95 *GPC-DRI asdescribed below, **(g polymer/g cat*hr)GPC-DRI for Samples in Table 1.

Gel permeation chromatography was performed on a Waters Alliance GPC,2000 equipped with a differential refractive index (DRI) detector. Thesolvent consisted of 1,2,4-trichlorobenzene (Sigma Aldrich, Chromasolvgrade ≥99% purity) stabilized with 1000 ppm of2,6-di-tert-butyl-4-methylphenol (Sigma Aldrich). The solvent wasfiltered using a membrane filter (Millipore, polytetrafluoroethylene,0.1 μm) prior to use. All samples were dissolved at a concentration ofapproximately 0.25 to 1.5 mg/mL in this solvent. Dissolution was carriedout at 160° C. in a shaker oven for 2-3 hours. The samples wereimmediately transferred to a sample carousel maintained at 160° C.Separation was effected by three TSK gel columns in series (TosohBioscience LLC, TSK gel GMH_(HR)-H(30)HT2, 300 mm×7.8 mm, 30 μm) at 160°C. The solvent was passed through an in-line filter (OptimizeTechnologies, SS frit, 2 μm) prior to entering the columns at anisocratic flow of 1.0 mL/min. Molecular weight was determined by auniversal calibration as described below using a set of seventeen narrowpolystyrene standards (Agilent Technologies) with peak molecular weights(Mp) from ˜1000 to ˜10,000,000 g/mol and Mw/Mn≤1.10. Mp for thepolystyrene standard provided on the certificate of analysis from themanufacturer was used for calibration. The universal calibration curvewas generated by fitting a second order polynomial to a plot of the logMp vs. retention volume for the polystyrene standards in Microsoft Excel(Version 14.0.7113.5000). Using this calibration and the Mark-Houwinkexpression, molecular weight moments were determined for polyolefins ofknown composition. The composition used for GPC analysis is determinedby ¹H NMR.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including.” Likewise whenever a composition,an element or a group of elements is preceded with the transitionalphrase “comprising,” it is understood that we also contemplate the samecomposition or group of elements with transitional phrases “consistingessentially of,” “consisting of,” “selected from the group of consistingof,” or “is” preceding the recitation of the composition, element, orelements and vice versa.

What is claimed is:
 1. A catalyst system comprising: 1) supportcomprising inorganic oxide and an organoaluminum treated layeredsilicate and 2) pyridyldiamido compound represented by the Formula (A):

wherein: M* is a Group 4 metal; each E′ group is independently selectedfrom carbon, silicon, or germanium; each X′ is an anionic leaving group;L* is a neutral Lewis base; R′¹ and R′¹³ are independently selected fromthe group consisting of hydrocarbyls, substituted hydrocarbyls, andsilyl groups; R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, andR′¹² are independently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphine; n′ is 1 or 2; m′ is 0, 1, or 2; and two X′groups may be joined together to form a dianionic group; two L* groupsmay be joined together to form a bidentate Lewis base; an X′ group maybe joined to an L* group to form a monoanionic bidentate group; R′⁷ andR′⁸ may be joined to form a ring; and R′¹⁰ and R′¹¹ may be joined toform a ring.
 2. The catalyst system of claim 1, wherein the support ispresent in the form of spherioid particles, has an average aspect ratio(L/W) of 1 to 1.7; has an average particle size (D50) of 20 to 180microns, has a surface area of about 100 to about 200 m²/g and has apore volume of about 0.1 to about 0.4 cc/g.
 3. The catalyst system ofclaim 1, wherein the catalyst system has an average aspect ratio (L/W)of 1 to 1.7, has an average particle size (D50) of 20 to 180 microns,and has a pore volume of about 0.1 to about 0.4 cc/g.
 4. The catalystsystem of claim 1, wherein the support comprises particles of anagglomerate of an inorganic oxide and treated layered silicate, wherethe support comprising inorganic oxide and an organoaluminum treatedlayered silicate has been spray dried prior to contact with theorganoaluminum.
 5. The catalyst system of claim 4, wherein the supportis obtained by spray drying an aqueous slurry of layered silicate and aninorganic oxide, where a pH of the slurry is from about 3 to 7; a drysolids content of the slurry is from about 20 to 30 wt % based on theweight of the slurry and the dry weight of the solids; a ratio ofinorganic oxide to layered silicate in the slurry is from 1:5 to 1:20;and the spray dried support has an average particle size of from 20 to125 microns and is free flowing.
 6. A catalyst system comprising: 1)support comprising inorganic oxide and an organoaluminum treated layeredsilicate and 2) pyridyldiamido compound represented by the Formula (I):

wherein: M is a Group 4 metal; Z is —(R¹⁴)_(p)C—C(R¹⁵)_(q)—, where R¹⁴and R¹⁵ are independently selected from the group consisting ofhydrogen, hydrocarbyls, and substituted hydrocarbyls, and whereinadjacent R¹⁴ and R¹⁵ groups may be joined to form an aromatic orsaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ringcan join to form additional rings, p is 0, 1, or 2, and q is 0, 1, or 2;R¹ and R¹¹ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups; R² and R¹⁰ areeach, independently, -E(R¹²)(R¹³)— with E being carbon, silicon, orgermanium, and each R¹² and R¹³ being independently selected from thegroup consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino,aryloxy, substituted hydrocarbyls, halogen, and phosphine, R¹² and R¹³may be joined to each other or to R¹⁴ or R¹⁵ to form a saturated,substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5,6, or 7 ring carbon atoms and where substitutions on the ring can jointo form additional rings, or R¹² and R¹³ may be joined to form asaturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings;R³, R⁴, and R⁵ are independently selected from the group consisting ofhydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy,halogen, amino, and silyl, and wherein adjacent R groups (R³ & R⁴ and/orR⁴ & R⁵) may be joined to form a substituted or unsubstitutedhydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ringatoms and where substitutions on the ring can join to form additionalrings; L is an anionic leaving group, where the L groups may be the sameor different and any two L groups may be linked to form a dianionicleaving group; n is 0, 1, 2, or 3; L′ is a neutral Lewis base; and w is0, 1, 2, or
 3. 7. The catalyst system of claim 6 wherein: A) the supportis obtained by spray drying an aqueous slurry of alkylaluminum treatedlayered silicate and an inorganic oxide comprising a Group 1 or 2silicate; and 1) the support comprises particles having an averagediameter of 20 to 100 microns, and/or 2) the support comprises particleshaving a pore volume of between 0.1 and 0.4 cc/g, and/or 3) the supportcomprises particles having a surface area of between 100 and 200 m²/g;and B) the organoaluminum comprises trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,triisooctylaluminum, triphenylaluminum, or a combination thereof.
 8. Acatalyst system comprising: 1) support comprising inorganic oxide and anorganoaluminum treated layered silicate and 2) pyridyldiamido compoundrepresented by the Formula III:

wherein: R⁶, R⁷, R⁸, R⁹, R¹⁶, and R¹⁷ are independently selected fromthe group consisting of hydrogen, hydrocarbyls, substitutedhydrocarbyls, alkoxy, halogen, amino, and silyl, wherein adjacent Rgroups (R⁶ & R⁷, and/or R⁷ & R¹⁶, and/or R¹⁶ & R¹⁷, and/or R⁸ & R⁹) maybe joined to form a saturated, substituted or unsubstituted hydrocarbylor heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atomsand where substitutions on the ring can join to form additional rings; Mis a Group 4 metal; R¹ and R¹¹ are independently selected from the groupconsisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;R² and R¹⁰ are each, independently, -E(R¹²)(R¹³)— with E being carbon,silicon, or germanium, and each R¹² and R¹³ being independently selectedfrom the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl,amino, aryloxy, substituted hydrocarbyls, halogen, and phosphine, R¹²and R¹³ may be joined to each other to form a saturated, substituted orunsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ringcarbon atoms and where substitutions on the ring can join to formadditional rings, or R¹² and R¹³ may be joined to form a saturatedheterocyclic ring, or a saturated substituted heterocyclic ring wheresubstitutions on the ring can join to form additional rings; R³, R⁴, andR⁵ are independently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino,and silyl, and wherein adjacent R groups (R³ & R⁴ and/or R⁴ & R⁵) may bejoined to form a substituted or unsubstituted hydrocarbyl orheterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and wheresubstitutions on the ring can join to form additional rings; L is ananionic leaving group, where the L groups may be the same or differentand any two L groups may be linked to form a dianionic leaving group; nis 0, 1, 2, or 3; L′ is a neutral Lewis base; and w is 0, 1, 2, or
 3. 9.The catalyst system of claim 8 wherein: A) the support is obtained byspray drying an aqueous slurry of alkylaluminum treated layered silicateand an inorganic oxide comprising a Group 1 or 2 silicate; and 1) thesupport comprises particles having an average diameter of 20 to 100microns, and/or 2) the support comprises particles having a pore volumeof between 0.1 and 0.4 cc/g, and/or 3) the support comprises particleshaving a surface area of between 100 and 200 m²/g; and B) theorganoaluminum comprises trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,triisooctylaluminum, triphenylaluminum, or a combination thereof.
 10. Aprocess to polymerize olefins comprising: i) contacting olefins with acatalyst system comprising: 1) support comprising: a) an organoaluminumtreated layered silicate, and b) inorganic oxide, and 2) pyridyldiamidocompound represented by the Formula (A):

wherein: M* is a Group 4 metal; each E′ group is independently selectedfrom carbon, silicon, or germanium; each X′ is an anionic leaving group;L* is a neutral Lewis base; R′¹ and R′¹³ are independently selected fromthe group consisting of hydrocarbyls, substituted hydrocarbyls, andsilyl groups; R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, andR′¹² are independently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphine; n′ is 1 or 2; m′ is 0, 1, or 2; and two X′groups may be joined together to form a dianionic group; two L* groupsmay be joined together to form a bidentate Lewis base; an X′ group maybe joined to an L* group to form a monoanionic bidentate group; R′⁷ andR′⁸ may be joined to form a ring; and R′¹⁰ and R′¹¹ may be joined toform a ring; ii) obtaining a polyolefin composition.
 11. The process ofclaim 10, wherein a combination of layered silicate and inorganic oxideis spray dried prior to contact with the organoaluminum.
 12. The processof claim 10, wherein the support is obtained by spray drying an aqueousslurry of alkylaluminum treated layered silicate and an inorganic oxidecomprising a Group 1 or 2 silicate.
 13. The process of claim 10, whereinthe support is obtained by spray drying an aqueous slurry of trialkylaluminum treated montmorillonite, where the alkyl is a C1 to C12 alkylgroup, and a sodium, potassium, lithium or magnesium silicate, or amixture thereof.
 14. The process of claim 10, wherein the supportcomprises spheroidal particles of a combination of the organoaluminumtreated layered silicate and the inorganic oxide.
 15. The process ofclaim 10, wherein: 1) the support comprises particles having an averagediameter of 20 to 100 microns, and/or 2) the support comprises particleshaving a pore volume of between 0.1 and 0.4 cc/g, and/or 3) the supportcomprises particles having a surface area of between 100 and 200 m²/g.16. The process of claim 10, wherein the support comprises at least 10wt % montmorillonite, based upon the weight of the organoaluminumtreated layered silicate and the inorganic oxide.
 17. The process ofclaim 10, wherein the organoaluminum comprises trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, triisooctylaluminum, triphenylaluminum, or acombination thereof.
 18. The process of claim 10, wherein the supportand/or the catalyst system has an average aspect ratio (L/W) of 1 to1.7.
 19. The process of claim 10, wherein the support is obtained byspray drying an aqueous slurry of layered silicate and inorganic oxide,where a pH of the slurry is from about 3 to 7; a dry solids content ofthe aqueous slurry is from about 20 to 30 wt % based on the weight ofthe slurry and the dry weight of the solids; and a ratio of inorganicoxide to layered silicate is in the range of 1:5 to 1:20.
 20. Theprocess of claim 19, wherein the spray dried combination has an averageparticle size of from 20 to 125 microns and is free flowing.
 21. Theprocess of claim 10, wherein the support comprises 50 to 90 wt %montmorillonite, based upon the weight of the organoaluminum treatedlayered silicate and the inorganic oxide.
 22. The process of claim 10,wherein alumoxane and/or non-coordinating anion is absent.
 23. Theprocess of claim 10, wherein the process to polymerize olefins isconducted in the gas phase or the slurry phase.
 24. The process of claim10, wherein the polyolefin composition, has an Mw of 1,000,000 g/mol ormore and comprises at least 0.1 wt % of the layered silicate, wherepolyolefin composition A has: 1) no diffraction peak resulting frominterlamellar spacing of the organoaluminum treated layered silicate, or2) a diffraction peak resulting from interlamellar spacing of theorganoaluminum treated layered silicate of Z Angstroms or more, whereZ=5X, where X is the diffraction peak resulting from interlamellarspacing of the support before combination with the catalyst compound, asmeasured by wide angle x-ray scattering.
 25. The process of claim 10,wherein the polyolefin composition has no diffraction peak resultingfrom interlamellar spacing of the organoaluminum treated layeredsilicate.
 26. The process of claim 10, wherein the polyolefincomposition is an ethylene polymer.
 27. The process of claim 10, whereinthe polyolefin composition is an ethylene homopolymer.
 28. The processof claim 10, wherein the polyolefin composition is an ethylenecopolymer.
 29. The process of claim 10, wherein the polyolefincomposition has an Mw from 1,000,000 to 3,000,000 g/mol.
 30. A processto polymerize olefins comprising: i) contacting olefins with a catalystsystem comprising: 1) support comprising inorganic oxide and anorganoaluminum treated layered silicate and 2) pyridyldiamido compoundrepresented by the Formula (A):

wherein: M* is a Group 4 metal; each E′ group is independently selectedfrom carbon, silicon, or germanium; each X′ is an anionic leaving group;L* is a neutral Lewis base; R′¹ and R′¹³ are independently selected fromthe group consisting of hydrocarbyls, substituted hydrocarbyls, andsilyl groups; R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, andR′¹² are independently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphine; n′ is 1 or 2; m′ is 0, 1, or 2; and two X′groups may be joined together to form a dianionic group; two L* groupsmay be joined together to form a bidentate Lewis base; an X′ group maybe joined to an L* group to form a monoanionic bidentate group; R′⁷ andR′⁸ may be joined to form a ring; and R′¹⁰ and R′¹¹ may be joined toform a ring; and ii) obtaining a polyolefin composition having an Mw of1,000,000 g/mol or more and comprising 5 wt % or less of the layeredsilicate, where the polyolefin composition has: 1) no diffraction peakresulting from interlamellar spacing of the organoaluminum treatedlayered silicate, or 2) a diffraction peak resulting from interlamellarspacing of the organoaluminum treated layered silicate of Z Angstroms ormore, where Z=5X, where X is the diffraction peak resulting frominterlamellar spacing of the support before combination with thecatalyst compound, as measured by wide angle x-ray scattering.
 31. Aprocess to polymerize olefins comprising: i) contacting olefinscomprising ethylene with a catalyst system comprising: 1) supportcomprising: a) an organoaluminum treated layered silicate, and b)inorganic oxide, and 2) pyridyldiamido compound represented by theFormula (A):

wherein: M* is a Group 4 metal; each E′ group is independently selectedfrom carbon, silicon, or germanium; each X′ is an anionic leaving group;L* is a neutral Lewis base; R′¹ and R′¹³ are independently selected fromthe group consisting of hydrocarbyls, substituted hydrocarbyls, andsilyl groups; R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, andR′¹² are independently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphine; n′ is 1 or 2; m′ is 0, 1, or 2; and two X′groups may be joined together to form a dianionic group; two L* groupsmay be joined together to form a bidentate Lewis base; an X′ group maybe joined to an L* group to form a monoanionic bidentate group; R′⁷ andR′⁸ may be joined to form a ring; and R′¹⁰ and R′¹¹ may be joined toform a ring; ii) obtaining an ethylene polymer having an Mw of 1,000,000g/mol or more and comprising 0.1 to 5 wt % of a layered silicate, wherethe ethylene polymer has no diffraction peak resulting frominterlamellar spacing of the layered silicate, as measured by wide anglex-ray scattering.
 32. A process to polymerize olefins comprising: i)contacting olefins comprising ethylene with a catalyst systemcomprising: 1) support comprising: a) an organoaluminum treated layeredsilicate, and b) an organoaluminum treated inorganic oxide, and 2)pyridyldiamido compound represented by the Formula (A):

wherein: M* is a Group 4 metal; each E′ group is independently selectedfrom carbon, silicon, or germanium; each X′ is an anionic leaving group;L* is a neutral Lewis base; R′¹ and R′¹³ are independently selected fromthe group consisting of hydrocarbyls, substituted hydrocarbyls, andsilyl groups; R′², R′³, R′⁴, R′⁵, R′⁶, R′⁷, R′⁸, R′⁹, R′¹⁰, R′¹¹, andR′¹² are independently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphine; n′ is 1 or 2; m′ is 0, 1, or 2; and two X′groups may be joined together to form a dianionic group; two L* groupsmay be joined together to form a bidentate Lewis base; an X′ group maybe joined to an L* group to form a monoanionic bidentate group; R′⁷ andR′⁸ may be joined to form a ring; and R′¹⁰ and R′¹¹ may be joined toform a ring; ii) obtaining an ethylene polymer having an Mw of 1,000,000g/mol or more and comprising 0.1 to 5 wt % of a layered silicate, wherethe ethylene polymer has no diffraction peak resulting frominterlamellar spacing of the layered silicate, as measured by wide anglex-ray scattering.
 33. A process to polymerize olefins comprising: i)contacting olefins with a catalyst system comprising: 1) supportcomprising: a) an organoaluminum treated layered silicate, and b)inorganic oxide, and 2) pyridyldiamido compound represented by theFormula (I):

wherein: M is a Group 4 metal; Z is —(R¹⁴)_(p)C—C(R¹⁵)_(q)—, where R¹⁴and R¹⁵ are independently selected from the group consisting ofhydrogen, hydrocarbyls, and substituted hydrocarbyls, and whereinadjacent R¹⁴ and R¹⁵ groups may be joined to form an aromatic orsaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ringcan join to form additional rings, p is 0, 1, or 2, and q is 0, 1, or 2;R¹ and R¹¹ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups; R² and R¹⁰ areeach, independently, -E(R¹²)(R¹³)— with E being carbon, silicon, orgermanium, and each R¹² and R¹³ being independently selected from thegroup consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino,aryloxy, substituted hydrocarbyls, halogen, and phosphine, R¹² and R¹³may be joined to each other or to R¹⁴ or R¹⁵ to form a saturated,substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5,6, or 7 ring carbon atoms and where substitutions on the ring can jointo form additional rings, or R¹² and R¹³ may be joined to form asaturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings;R³, R⁴, and R⁵ are independently selected from the group consisting ofhydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy,halogen, amino, and silyl, and wherein adjacent R groups (R³ & R⁴ and/orR⁴ & R⁵) may be joined to form a substituted or unsubstitutedhydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ringatoms and where substitutions on the ring can join to form additionalrings; L is an anionic leaving group, where the L groups may be the sameor different and any two L groups may be linked to form a dianionicleaving group; n is 0, 1, 2, or 3; L′ is a neutral Lewis base; and w is0, 1, 2, or 3; and ii) obtaining a polyolefin composition.
 34. Theprocess of claim 33, wherein M is zirconium or hafnium.
 35. The processof claim 33, wherein each of R¹, R³, R⁴, R⁵, and R¹¹ is, independently,hydrogen or a hydrocarbyl.
 36. The process of claim 33, wherein M ishafnium.
 37. The process of claim 33, wherein M is zirconium or hafnium.38. The process of claim 33, wherein each of R² and R¹⁰ isindependently, -E(R¹²)(R¹³)— with E being carbon and each R′² and R¹³being independently selected from the group consisting of hydrocarbyls.39. A process to polymerize olefins comprising: i) contacting olefinswith a catalyst system comprising: 1) support comprising: a) anorganoaluminum treated layered silicate, and b) inorganic oxide, and 2)pyridyldiamido compound represented by Formula II:

wherein: R⁶, R⁷, R⁸, and R⁹ are independently selected from the groupconsisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy,halogen, amino, and silyl, and wherein adjacent R groups (R⁶& R⁷, and/orR⁷& R⁸, and/or R⁸& R⁹, and/or R⁹& R¹⁰) may be joined to form asaturated, substituted or unsubstituted hydrocarbyl or heterocyclicring, where the ring has 5, 6, 7, or 8 ring carbon atoms and wheresubstitutions on the ring can join to form additional rings; M is aGroup 4 metal; R¹ and R¹¹ are independently selected from the groupconsisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;R² and R¹⁰ are each, independently, -E(R¹²)(R¹³)— with E being carbon,silicon, or germanium, and each R¹² and R¹³ being independently selectedfrom the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl,amino, aryloxy, substituted hydrocarbyls, halogen, and phosphine, R¹²and R¹³ may be joined to each other to form a saturated, substituted orunsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ringcarbon atoms and where substitutions on the ring can join to formadditional rings, or R¹² and R¹³ may be joined to form a saturatedheterocyclic ring, or a saturated substituted heterocyclic ring wheresubstitutions on the ring can join to form additional rings; R³, R⁴, andR⁵ are independently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino,and silyl, and wherein adjacent R groups (R³ & R⁴ and/or R⁴ & R⁵) may bejoined to form a substituted or unsubstituted hydrocarbyl orheterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and wheresubstitutions on the ring can join to form additional rings; L is ananionic leaving group, where the L groups may be the same or differentand any two L groups may be linked to form a dianionic leaving group; nis 0, 1, 2, or 3; L′ is a neutral Lewis base; and w is 0, 1, 2, or 3;and ii) obtaining a polyolefin composition.
 40. A process to polymerizeolefins comprising: i) contacting olefins with a catalyst systemcomprising: 1) support comprising: a) an organoaluminum treated layeredsilicate, and b) inorganic oxide, and 2) pyridyldiamido compoundrepresented by Formula III:

wherein: R⁶, R⁷, R⁸, R⁹, R¹⁶, and R¹⁷ are independently selected fromthe group consisting of hydrogen, hydrocarbyls, substitutedhydrocarbyls, alkoxy, halogen, amino, and silyl, wherein adjacent Rgroups (R⁶ & R⁷, and/or R⁷ & R¹⁶, and/or R¹⁶ & R¹⁷, and/or R⁸ & R⁹) maybe joined to form a saturated, substituted or unsubstituted hydrocarbylor heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atomsand where substitutions on the ring can join to form additional rings; Mis a Group 4 metal; R¹ and R¹¹ are independently selected from the groupconsisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;R² and R¹⁰ are each, independently, -E(R¹²)(R¹³)— with E being carbon,silicon, or germanium, and each R¹² and R¹³ being independently selectedfrom the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl,amino, aryloxy, substituted hydrocarbyls, halogen, and phosphine, R¹²and R¹³ may be joined to each other to form a saturated, substituted orunsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ringcarbon atoms and where substitutions on the ring can join to formadditional rings, or R¹² and R¹³ may be joined to form a saturatedheterocyclic ring, or a saturated substituted heterocyclic ring wheresubstitutions on the ring can join to form additional rings; R³, R⁴, andR⁵ are independently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino,and silyl, and wherein adjacent R groups (R³ & R⁴ and/or R⁴ & R⁵) may bejoined to form a substituted or unsubstituted hydrocarbyl orheterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and wheresubstitutions on the ring can join to form additional rings; L is ananionic leaving group, where the L groups may be the same or differentand any two L groups may be linked to form a dianionic leaving group; nis 0, 1, 2, or 3; L′ is a neutral Lewis base; and w is 0, 1, 2, or 3;and ii) obtaining a polyolefin composition.
 41. The process of claim 40,wherein a combination of layered silicate and inorganic oxide is spraydried prior to contact with the organoaluminum.
 42. The process of claim40, wherein the support is obtained by spray drying an aqueous slurry ofalkylaluminum treated layered silicate and an inorganic oxide comprisinga Group 1 or 2 silicate.
 43. The process of claim 40, wherein thesupport is obtained by spray drying an aqueous slurry of trialkylaluminum treated montmorillonite, where the alkyl is a C1 to C12 alkylgroup, and a sodium, potassium, lithium or magnesium silicate, or amixture thereof.
 44. The process of claim 40, wherein: 1) the supportcomprises particles having an average diameter of 20 to 100 microns,and/or 2) the support comprises particles having a pore volume ofbetween 0.1 and 0.4 cc/g, and/or 3) the support comprises particleshaving a surface area of between 100 and 200 m²/g.
 45. The process ofclaim 40, wherein the organoaluminum comprises trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, triisooctylaluminum, triphenylaluminum, or acombination thereof.
 46. The process of claim 40, wherein alumoxaneand/or non-coordinating anion is absent.
 47. The process of claim 40,wherein the polyolefin composition is an ethylene polymer.
 48. Anethylene polymer having an Mw of 1,000,000 g/mol or more and comprising0.1 to 5 wt % of a layered silicate, where the ethylene polymer has nodiffraction peak resulting from interlamellar spacing of the layeredsilicate, as measured by wide angle x-ray scattering.
 49. An ethylenepolymer having an Mw of 1,000,000 g/mol or more and comprising 0.1 to 5wt % of a layered silicate derived from a supported catalyst used toproduce the ethylene polymer, where the ethylene polymer has 1) nodiffraction peak resulting from interlamellar spacing of the layeredsilicate present in the supported catalyst or 2) a diffraction peakresulting from interlamellar spacing of the layered silicate of ZAngstroms or more, where Z=5X, where X is the diffraction peak resultingfrom interlamellar spacing of the layered silicate present in thesupported catalyst, as measured by wide angle x-ray scattering.